Method for manufacturing positive electrode active material, and lithium ion battery

ABSTRACT

A composite oxide with high diffusion rate of lithium is provided. Alternatively, a lithium-containing complex phosphate with high diffusion rate of lithium is provided. Alternatively, a positive electrode active material with high diffusion rate of lithium is provided. Alternatively, a lithium ion battery with high output is provided. Alternatively, a lithium ion battery that can be manufactured at low cost is provided. A positive electrode active material is formed through a first step of mixing a lithium compound, a phosphorus compound, and water, a second step of adjusting pH by adding a first aqueous solution to a first mixed solution formed in the first step, a third step of mixing an iron compound with a second mixed solution formed in the second step, a fourth step of performing heat treatment under a pressure more than or equal to 0.1 MPa and less than or equal to 2 MPa at a highest temperature more than 100° C. and less than or equal to 119° C. on a third mixed solution formed in the third step with a pH of more than or equal to 3.5 and less than or equal to 5.0.

BACKGROUND OF THE INVENTION 1. Field of the Invention

The present invention relates to an object, a method, or a manufacturingmethod. The present invention relates to a process, a machine,manufacture, or a composition of matter. In particular, one embodimentof the present invention relates to a semiconductor device, a displaydevice, a light-emitting device, a power storage device, a memorydevice, a driving method thereof, a manufacturing method thereof, or anevaluation method thereof. In particular, one embodiment of the presentinvention relates to a power storage device, a manufacturing methodthereof, and an evaluation method thereof. Alternatively, the presentinvention relates to a lithium-containing complex phosphate and amanufacturing method thereof. Alternatively, the present inventionrelates to a positive electrode active material and a manufacturingmethod thereof. Alternatively, the present invention relates to alithium ion battery. Alternatively, the present invention relates to abattery management unit and an electronic device.

2. Description of the Related Art

The solubility in a solution at high temperature and under high pressureis higher than at normal temperature and under normal pressure. Further,by controlling pH of the solution, the dissolution and precipitation ofa material can be controlled (Patent Document 1). As an example of areaction at high temperature and under high pressure, a hydrothermalmethod can be raised.

In recent years, power storage devices such as lithium ion secondarybatteries have been developed. Examples of such power storage devicesinclude a power storage device having an electrode formed using lithiumiron phosphate (LiFePO₄), which is a composite oxide, as an activematerial. The power storage device having an electrode formed usingLiFePO₄ has high thermal stability and favorable cycle characteristics.

As an example of a method for generating a composite oxide such asLiFePO₄, the hydrothermal method can be used (e.g., Patent Document 2).

By using the hydrothermal method, even a material which is less likelyto be dissolved in water at normal temperatures and under normalpressures can be dissolved, and thus a substance which is hardlyobtained by a production method performed at normal temperatures andunder normal pressures can be synthesized or crystal growth of such asubstance can be conducted. Further, by using the hydrothermal method,microparticles of single crystals of a target substance can be easilysynthesized.

The hydrothermal method, for example, enables a desired compound to begenerated in the following manner: a solution containing a raw materialis introduced into a container resistant to pressure and be subjected topressure treatment and heat treatment; and the treated solution isfiltered.

REFERENCES

[Patent Document 1] PCT International Publication No. 2008/091578

[Patent Document 2] Japanese Published Patent Application No. 2004-95385

SUMMARY OF THE INVENTION

An object of one embodiment of the present invention is to provide acomposite oxide with high diffusion rate of lithium. Another object ofone embodiment of the present invention is to provide alithium-containing complex phosphate with high diffusion rate oflithium. Another object of one embodiment of the present invention is toprovide a positive electrode active material with high diffusion rate oflithium. Another object of one embodiment of the present invention is toprovide a lithium ion battery with high output. Another object of oneembodiment of the present invention is to provide a lithium ion batterythat can be manufactured at low cost. Another object of one embodimentof the present invention is to provide a novel battery.

Note that the descriptions of these objects do not disturb the existenceof other objects. In one embodiment of the present invention, there isno need to achieve all the objects. Other objects will be apparent fromand can be derived from the description of the specification, thedrawings, the claims, and the like.

One embodiment of the present invention is a method for manufacturing apositive electrode active material including lithium, phosphorus, iron,and oxygen, including a first step of mixing a lithium compound, aphosphorus compound, and water, a second step of adjusting pH by addinga first aqueous solution to a first mixed solution formed in the firststep, a third step of mixing an iron compound with a second mixedsolution formed in the second step, and a fourth step of performing heattreatment under a pressure more than or equal to 0.1 MPa and less thanor equal to 2 MPa on a third mixed solution formed in the third step. ApH of the third mixed solution is more than or equal to 3.5 and lessthan or equal to 5.0, a highest temperature in the fourth step is morethan 100° C. and less than or equal to 119° C., and the positiveelectrode active material belongs to a space group Pnma.

In the above structure, the lithium compound is preferably a lithiumchloride, the first aqueous solution is preferably alkaline, and a baseincluded in the first aqueous solution is preferably ammonia or organicamine.

In the above structure, the third step is preferably performed in an airatmosphere.

In the above structure, a thickness of a particle of the positiveelectrode active material is preferably more than or equal to 10 nm andless than or equal to 200 nm.

Another embodiment of the present invention is a lithium ion batteryincluding the positive electrode active material manufactured accordingto any one of the above descriptions.

One embodiment of the present invention can provide a composite oxidewith high diffusion rate of lithium. Another embodiment of the presentinvention can provide a lithium-containing complex phosphate with highdiffusion rate of lithium. Another embodiment of the present inventioncan provide a positive electrode active material with high diffusionrate of lithium. Another embodiment of the present invention can providea lithium ion battery with high output. Another embodiment of thepresent invention can provide a lithium ion battery that can bemanufactured at low cost. Another embodiment of the present inventioncan provide a novel battery.

Note that one embodiment of the present invention is not limited tothese effects. For example, depending on circumstances or conditions,one embodiment of the present invention might produce another effect.Furthermore, depending on circumstances or conditions, one embodiment ofthe present invention might not produce any of the above effects.

BRIEF DESCRIPTION OF THE DRAWINGS

In the accompanying drawings:

FIG. 1 is a flowchart of a method for manufacturing a lithium-containingcomplex phosphate;

FIG. 2 is a flowchart of a method for manufacturing a lithium-containingcomplex phosphate;

FIGS. 3A and 3B are each a perspective view illustrating an example of aparticle;

FIGS. 4A and 4B are diagrams illustrating part of a cross section of anelectrode;

FIG. 5 illustrates a storage battery;

FIGS. 6A and 6B are cross-sectional views illustrating storagebatteries;

FIGS. 7A and 7B illustrate a method for manufacturing a storage battery;

FIGS. 8A and 8B show a method for manufacturing a storage battery;

FIG. 9 illustrates a storage battery;

FIG. 10A to 10C illustrate the radius of curvature of a surface;

FIGS. 11A to 11D illustrate the radius of curvature of a film;

FIGS. 12A and 12B illustrate a coin-type storage battery;

FIGS. 13A and 13B illustrate a cylindrical storage battery;

FIGS. 14A to 14C are each a part of a cross-sectional view of a storagebattery;

FIGS. 15A and 15B are each a part of a cross-sectional view of a storagebattery;

FIGS. 16A to 16C are each a part of a cross-sectional view of a storagebattery;

FIGS. 17A to 17C illustrate an example of a storage battery;

FIGS. 18A to 18C illustrate an example of a storage battery;

FIGS. 19A and 19B illustrate an example of a power storage system;

FIGS. 20A1, 20A2, 20B1, and 20B2 illustrate examples of power storagesystems;

FIGS. 21A and 21B each illustrate an example of a power storage system;

FIGS. 22A to 22G illustrate examples of electronic devices;

FIGS. 23A to 23C illustrate examples of electronic devices;

FIG. 24 illustrates examples of electronic devices;

FIGS. 25A and 25B illustrate examples of electronic devices;

FIGS. 26A and 26B show XRD evaluation results;

FIGS. 27A and 27B show XRD evaluation results;

FIGS. 28A and 28B show XRD evaluation results;

FIGS. 29A and 29B show XRD evaluation results;

FIG. 30 shows XRD evaluation results;

FIG. 31 shows XRD evaluation results;

FIGS. 32A and 32B show SEM observation results;

FIGS. 33A and 33B show SEM observation results;

FIGS. 34A and 34B show SEM observation results;

FIGS. 35A and 35B show SEM observation results;

FIGS. 36A and 36B show SEM observation results;

FIGS. 37A and 37B show SEM observation results;

FIGS. 38A and 38B show SEM observation results; and

FIGS. 39A and 39B show SEM observation results.

DETAILED DESCRIPTION OF THE INVENTION

Embodiments of the present invention will be described in detail belowwith reference to the accompanying drawings. However, the presentinvention is not limited to the descriptions of the embodiments and itis easily understood by those skilled in the art that the mode anddetails can be changed variously. Accordingly, the present inventionshould not be interpreted as being limited to the descriptions of theembodiments below.

Note that in drawings used in this specification, the sizes,thicknesses, and the like of components such as films, layers,substrates, and regions are exaggerated for simplicity in some cases.Therefore, the sizes of the components are not limited to the sizes inthe drawings and relative sizes between the components.

Note that the ordinal numbers such as “first” and “second” in thisspecification and the like are used for convenience and do not denotethe order of steps, the stacking order of layers, or the like.Therefore, for example, description can be made even when “first” isreplaced with “second” or “third”, as appropriate. In addition, theordinal numbers in this specification and the like are not necessarilythe same as those which specify one embodiment of the present invention.

Note that in structures of the present invention described in thisspecification and the like, the same portions or portions having similarfunctions are denoted by common reference numerals in differentdrawings, and descriptions thereof are not repeated. Further, the samehatching pattern is applied to portions having similar functions, andthe portions are not especially denoted by reference numerals in somecases.

Note that in this specification and the like, a positive electrode and anegative electrode for a power storage device may be collectivelyreferred to as an electrode; in this case, the electrode refers to atleast one of the positive electrode and the negative electrode.

Embodiment 1

In this embodiment, a lithium-containing complex phosphate of oneembodiment of the present invention will be described.

The lithium-containing complex phosphate of one embodiment of thepresent invention is manufactured using a liquid phase method and morepreferably, a hydrothermal method. Further, by manufacturing thelithium-containing complex phosphate of one embodiment of the presentinvention at a lower temperature, particles of the lithium-containingcomplex phosphate having a more favorable shape can be obtained in somecases. For example, by manufacturing at a lower temperature, thelithium-containing complex phosphate having a flat shape or a columnarshape can be obtained in some cases.

A lithium ion battery of one embodiment of the present inventionpreferably includes the lithium-containing complex phosphate of oneembodiment of the present invention as an active material of anelectrode.

The lithium-containing complex phosphate is a flat-shaped particle,whereby the filling rate of an active material per unit volume in anelectrode using the lithium-containing complex phosphate as the activematerial can be higher in some cases than that of a spherical particle,for example. Here, the filling rate is the proportion of the volume ofthe active material to the total volume. Further, the lithium-containingcomplex phosphate is the flat-shaped particle, whereby output of thelithium ion battery can be high in some cases, for example. Here, “highoutput of lithium ion battery” means that a current density is high inat least one of charge and discharge.

Further, the lithium-containing complex phosphate of one embodiment ofthe present invention is manufactured at a lower temperature; thus,productivity of a manufacturing process can be improved. Further, bymanufacturing at a lower temperature, the lithium-containing complexphosphate can be manufactured at low cost in some cases.

Further, the lithium-containing complex phosphate of one embodiment ofthe present invention is preferably a particle, further preferably acolumnar-shaped particle, and still further preferably a flat-shapedparticle.

<Manufacturing Method>

A method for manufacturing the lithium-containing complex phosphateaccording to one embodiment of the present invention will be describedwith reference to FIG. 1.

In Step S201 a, a lithium compound is weighed. In Step S201 b, aphosphorus compound is weighed.

Here, the atomic ratio of lithium to metal M(II) to phosphorus of thelithium-containing complex phosphate preferably obtained as a syntheticmaterial A, described later, is x:y:z. The number of moles of lithium ofthe lithium compound weighed in Step S201 a is f, the number of moles ofphosphorus of the phosphorus compound weighed in Step S201 b is g, thenumber of moles of metal M(II) of the M(II) compound weighed in StepS201 c is h. Preferably, f/g is 1.5 times to 3.5 times as large as x/y,more preferably larger than 2.6 times and smaller than 3.4 times aslarge as x/y and preferably, h/g is 0.7 times to 1.3 times as large asz/y. Here, when x:y:z is 1:1:1, a lithium-containing complex phosphatehaving an olivine structure can be obtained, for example.

Typical examples of the lithium compound include lithium chloride(LiCl), lithium acetate (LiCH₃COO), lithium oxalate ((COOLi)₂), lithiumcarbonate (Li₂CO₃), and lithium hydroxide monohydrate (LiOH.H₂O).

Typical examples of the phosphorus compound are a phosphoric acid suchas orthophosphoric acid (H₃PO₄), and ammonium hydrogenphosphates such asdiammonium hydrogenphosphate ((NH₄)₂HPO₄) and ammoniumdihydrogenphosphate (NH₄H₂PO₄).

Next, in Step S201 d, a solvent is weighed. Water is preferably used asthe solvent. Further, a mixed solution containing water and anothersolvent may be used as the solvent. For example, water and alcohol maybe mixed. Here, the solubility of the lithium compound, the phosphoruscompound, and a reaction product of the lithium compound and thephosphorus compound in water and the solubility thereof in alcohol aredifferent in some cases. By using alcohol, the grain size of theparticle, which is to be formed, becomes smaller in some cases. Further,by using alcohol with a lower boiling point than water, pressure can beeasily increased in some cases in Step S211 described later.

Next, a mixed solution A is formed in Step S205. Mixing can be performedunder an atmosphere of air, inert gas, or the like. As the inert gas,nitrogen may be used, for example. Here, as an example, in an airatmosphere, the solvent weighed in Step S201 d, the lithium compoundweighed in Step S201 a, and the phosphorus compound weighed in Step S201b are mixed. For example, the lithium compound weighed in Step S201 aand the phosphorus compound weighed in Step S201 b are put in thesolvent weighed in Step S201 d, so that the mixed solution A is formed.In the case of forming the mixed solution A in the air atmosphere, anapparatus for controlling the atmosphere is not necessary, so that theprocess can be simplified and cost can be reduced as compared with thecase where inert gas is used.

It can be considered that in the mixed solution A, the lithium compound,the phosphorus compound, and the reaction product of the lithiumcompound and the phosphorus compound precipitate, but are partlydissolved without precipitating, i.e., partly exist in the solvent asions. Here, when the mixed solution A has a low pH, there are caseswhere the reaction product and the like are easily dissolved in thesolvent. When the mixed solution A has a high pH, there are cases wherethe reaction product and the like are easily precipitated in thesolvent.

Note that instead of forming the mixed solution A through Step S205, acompound including phosphorus and lithium such as Li₃PO₄, Li₂HPO₄, orLiH₂PO₄ is weighed and added to the solvent so that the mixed solution Amay be formed.

Here, in the case where the mixed solution A is an aqueous solution, pHof the mixed solution A is determined by the type and dissociationdegree of salt included in the mixed solution A. Thus, with the lithiumcompound and the phosphorus compound used as source materials, pH of themixed solution A changes. For example, in the case of using the lithiumchloride as the lithium compound and the orthophosphoric acid as thephosphorus compound, the mixed solution A is a strong acid. Further, forexample, in the case where the lithium hydroxide monohydrate is used asthe lithium compound, the mixed solution A is likely to be alkaline.

Next, the mixed solution A and a solution Q weighed in Step S205 b aremixed, so that a mixed solution B is formed in Step S207. Here, byadjusting the amount or concentration of the solution Q which is added,pH of the obtained mixed solution B and that of a later obtained mixedsolution C can be adjusted. In Step S207, while pH of the mixed solutionA is measured, the solution Q may be dropped, for example. As thesolution Q, the alkaline solution or the acid solution is used inaccordance with pH of the mixed solution A. By using a slightly alkalinesolution, or a slightly acidic solution, pH is easily adjusted in somecases. For example, a pH of the alkaline solution may be greater than orequal to 8 and less than or equal to 12. Further, a pH of the acidsolution may be greater than or equal to 2 and less than or equal to 6.As the alkaline solution, ammonia water may be used, for example. It ispreferable to determine pH of the solution Q so that the mixed solutionC, which is described later, is acidic or neutral. For example, in thecase of using the lithium chloride as the lithium compound and theorthophosphoric acid as the phosphorus compound, the solution Q may bealkaline.

In Step S208, one or more of an iron(II) compound, a manganese(II)compound, a cobalt(II) compound, and a nickel(II) compound (hereinafterreferred to as an M(II) compound) are weighed.

Typical examples of the iron(II) compound are iron chloride tetrahydrate(FeCl₂. 4H₂O), iron sulfate heptahydrate (FeSO₄.7H₂O), and iron acetate(Fe(CH₃COO)₂).

Typical examples of the manganese(II) compound are manganese chloridetetrahydrate (MnCl₂.4H₂O), manganese sulfate-hydrate (MnSO₄.H₂O), andmanganese acetate tetrahydrate (Mn(CH₃COO)₂.4H₂O).

Typical examples of the cobalt(II) compound are cobalt chloridehexahydrate (CoCl_(z).6H₂O), cobalt sulfate heptahydrate (CoSO₄.7H₂O),and cobalt acetate tetrahydrate (Co(CH₃COO)₂.4H₂O).

Typical examples of the nickel(II) compound are nickel chloridehexahydrate (NiCl_(z).6H₂O), nickel sulfate hexahydrate (NiSO₄.6H₂O),and nickel acetate tetrahydrate (Ni(CH₃COO)₂.4H₂O).

Next, the mixed solution C is formed in Step S209. Step S209 can beperformed under an atmosphere of air, inert gas, or the like. As theinert gas, nitrogen may be used, for example. Here, as an example, in anair atmosphere, the mixed solution A formed in Step S207 and the M(II)compound weighed in Step S208 are mixed so that the mixed solution C isformed. In the case of performing Step S209 in the air atmosphere, it ispreferable that Step S208 is performed right before Step S209, forexample, within 1 hour, further preferably within 20 minutes, stillfurther preferably within 10 minutes.

As illustrated in FIG. 2, the solvent may be added to adjust theconcentration of the mixed solution C in Step S209. In the flowchartillustrated in FIG. 2, after a mixture of the mixed solution B and theM(II) compound is formed, the solvent is weighed in Step S209 b and thesolvent and the mixture are mixed in Step S209 so that the mixedsolution C is manufactured.

Next, in Step S211, the mixed solution C is put into a heat and pressureresistant container such as an autoclave. Heating is performed at atemperature higher than or equal to 100° C. and lower than or equal to350° C., preferably higher than 100° C. and lower than 120° C. and undera pressure higher than or equal to 0.1 MPa and lower than or equal to100 MPa, preferably higher than or equal to 0.1 MPa and lower than orequal to 2 MPa for more than or equal to 0.5 hours and less than orequal to 24 hours, preferably more than or equal to 1 hour and less thanor equal to 10 hours, and further preferably more than or equal to 1hour and less than 5 hours and the solution is then cooled. The solutionin the heat and pressure resistant container is then filtered, followedby washing and drying. After that, the solution is separated. Forexample, filtration and washing are performed. Then, drying is performedin Step S213, and the synthetic material A is obtained.

As a result, a lithium-containing complex phosphate, more specifically,a lithium-containing complex phosphate having an olivine structure(LiMPO₄ (M is one or more of Fe(II), Ni(II), Co(II), and Mn(II))), forexample, can be obtained as a synthetic material A. As thelithium-containing complex phosphate, LiFePO₄, LiNiPO₄, LiCoPO₄,LiMnPO₄, LiFe_(a)Ni_(b)PO₄, LiFe_(a)Co_(b)PO₄, LiFe_(a)Mn_(b)PO₄,LiNi_(a)Co_(b)PO₄, LiNi_(a)Mn_(b)PO₄ (a+b≤1, 0<a<1, 0<b<1),LiFe_(c)Ni_(d)Co_(e)PO₄, LiFe_(c)Ni_(d)Mn_(e)PO₄,LiNi_(c)Co_(d)Mn_(e)PO₄ (c+d+e≤1, 0<c<1, 0<d<1, 0<e<1),LiFe_(f)Ni_(g)Co_(h)Mn_(i)PO₄ (f+g+h+i≤1, 0<f<1, 0<g<1, 0<h<1, 0<i<1),or the like can be obtained as appropriate depending on the type of theM(II) compound. The lithium-containing complex phosphate obtained inthis embodiment might be a single-crystal grain.

By performing crystal analysis such as XRD or electron diffraction onthe synthetic material A, the crystal structure can be identified. Byperforming crystal analysis on the synthetic material A, a crystalstructure belonging to a space group Pnma can be obtained in some cases.Here, LiMPO₄ having an olivine crystal structure belongs to the spacegroup Pnma, for example.

In Step S211, the reaction temperature is lowered so that thetemperature of the apparatus can be lowered. Further, the cost requiredfor the reaction can be reduced. As a result, productivity can beincreased. Further, the reaction temperature is lowered so that aflatter shape can be obtained as the particle of the synthetic materialA.

In FIG. 6 of Patent Document 1, a potential-pH diagram in the case ofiron is illustrated. As apparent from FIG. 6 of the Patent Document 1,in the case where pH is high, hydroxide of iron or oxide of iron isstable and in the case where pH is low, iron(II) ion is stable.

Further, the reaction temperature in Step S211 is lowered so that thespeed of the generation reaction of the synthetic material A is reducedand a by-product is easily generated in some cases. The generation ofthe by-product causes a reduction in yield. The by-product here, forexample, refers to a different compound from the synthetic material Athat is a target compound. The generation speed of the syntheticmaterial A is preferably higher than the generation speed of theby-product.

The mixed solution C is preferably an acid (in other words, pH islowered), so that the generation of the by-product can be suppressedeven in the case where the reaction temperature is lowered in Step S211.

In the case where pH of the mixed solution C is high, a large amount ofhydroxide ions is included. When pH of the mixed solution C is high, ahydroxide of an ion of a metal M is generated in some cases. From thehydroxide of the metal M here, an oxide of the metal M can be obtainedin some cases. For example, an iron ion and the hydroxide ion react witheach other to generate Fe(OH)₂, FeOOH can be generated from Fe(OH)₂, andFe₂O₃ can be generated from FeOOH in some cases.

Thus, in the mixed solution C, a by-reaction such as the generation ofthe hydroxide of the M ion occurs in some cases in addition to areaction of an M ion, a phosphorus ion, and a lithium ion for obtaininga lithium-containing complex phosphate that is preferable as thesynthetic material A.

By reducing pH of the mixed solution C, the by-reaction can besuppressed in some cases. On the other hand, when pH of the mixedsolution C is too low, the target synthetic material A dissolves in somecases. Alternatively, the synthetic material A is not generated in somecases.

By reducing pH of the mixed solution C, dissolution and generation ofthe particle are repeated. It can be considered that the dissolution ofa particle with low crystallinity is repeated and a particle with highcrystallinity is grown, for example. The flat-shaped particle or acolumnar-shaped particle as the particle with high crystallinity, forexample, can be easily obtained in some cases.

For example, a phosphate compound including iron with a differentvalence (including the hydrate) can be obtained as a by-product in somecases. Alternatively, for example, ammonium iron phosphate (includingthe hydrate) can be obtained as a by-product in some cases.

The mixed solution C has a pH, for example, higher than or equal to 1.0and lower than or equal to 8.0, further preferably higher than or equalto 2.0 and lower than or equal to 7.0, still further preferably higherthan or equal to 3.0 and lower than or equal to 6.0, still yet furtherpreferably higher than or equal to 3.5 and lower than or equal to 5.0.

In the case where iron is used as the element M, a pH of the mixedsolution C is preferably set higher than or equal to 3.0 and lower thanor equal to 6.0, further preferably higher than or equal to 3.5 andlower than or equal to 5.0, still further preferably higher than orequal to 3.5 and lower than or equal to 4.0 and the reaction temperaturein Step S211 is, for example, preferably set higher than 100° C. andlower than or equal to 119° C., further preferably higher than or equalto 103° C. and lower than or equal to 117° C., still further preferablyhigher than or equal to 105° C. and lower than or equal to 115° C.

Further, the generated by-product is preferably separated by filtration,for example, so that it is removed. For example, a solution in which theby-product is likely to be dissolved is prepared. After mixing with theobtained material in Step S211, filtration may be performed. Forexample, an acid solution can be given as an example of the solution.

<Particle Shape>

The lithium-containing complex phosphate of one embodiment of thepresent invention is preferably a particle and further preferably aflat-shaped particle.

Here, the flat-shaped particle includes a largest surface and athickness in a direction substantially perpendicular to the surface. Athickness 667 of the flat-shaped particle is, for example, more than orequal to 5 nm and less than or equal to 500 nm and preferably more thanor equal to 10 nm and less than or equal to 200 nm. The widest surfaceof the flat-shaped particle has a length 666 of more than or equal to 50nm and less than or equal to 3 μm. Alternatively, the length 666 is 3 to200 times the thickness 667 and preferably 10 to 50 times the thickness667. Here, the length of the surface may be, for example, the diameterof a circle obtained by converting the area of the surface. An exampleof a flat-shaped particle and examples of the length 666 and thethickness 667 are shown in FIGS. 3A and 3B. FIG. 3A shows a particle ina substantially flat polygonal-prism shape. FIG. 3B shows an example ofa particle including a largest surface with a curved side surface.

Preferably, the direction of the thickness 667 and the direction of theb axis are substantially parallel to each other and preferably, theangle between the direction of the thickness 667 and the direction ofthe b axis is more than or equal to 0° and less than or equal to 20° inthe case where the lithium-containing complex phosphate has an olivinestructure, for example. In the case where the thickness 667 and the baxis are substantially parallel, lithium can easily diffuse in thelithium-containing complex phosphate, so that output characteristics ofa storage battery are improved.

Alternatively, the lithium-containing complex phosphate of oneembodiment of the present invention may have a columnar shape. In thecase where the length of the cross section is larger than that of theheight, the lithium-containing complex phosphate has a flat shape, asdescribed above. In addition, preferably the b axis is substantiallyperpendicular to the height direction of the column, preferably thelength of the cross section is more than or equal to 5 nm and less thanor equal to 100 nm, and preferably the height is more than or equal to50 nm and less than or equal to 3 μm in the case where the length of thecross section is smaller than the height.

<XRD>

FIG. 29A shows the XRD measurement results obtained by a θ-2θ methodfrom the lithium-containing complex phosphate of one embodiment of thepresent invention described later in Example 1. Six peaks in totalhaving maximum values at 2θ of 17.1°, 20.7°, 25.5°, 29.8°, 32.1°, and35.6° in the range of 2θ from 17° to 36° can be observed as A to Fillustrated in FIG. 29A. The six peaks correspond to Power diffractionfile (PDF) Number 01-070-6684 of the International Centre forDiffraction Data (ICDD). Thus, it is suggested that thelithium-containing complex phosphate corresponds to LiFePO₄ in the spacegroup Pnma.

The lithium-containing complex phosphate of one embodiment of thepresent invention preferably includes peaks A, B, C, D, E, and F in theXRD measurement performed by the θ-2θ method. Note that in the casewhere the lithium-containing complex phosphate is aligned, one or moreof the six peaks A to F are difficult to observe in some cases. Thus,the lithium-containing complex phosphate of one embodiment of thepresent invention preferably includes two or more peaks, furtherpreferably three or more peaks, still further preferably all the sixpeaks of the six peaks A to F.

The degree of 2θ at which the peak A has the maximum value is A1 [° ]and the half width of the peak is A2 [°]. The degree of 2θ at which thepeak B has the maximum value is B1 [° ] and the half width of the peakis B2 [°]. The degree of 2θ at which the peak C has the maximum value isC1 [° ] and the half width of the peak is C2 [°]. The degree of 2θ atwhich the peak D has the maximum value is D1 [° ] and the half width ofthe peak is D2 [°]. The degree of 2θ at which the peak E has the maximumvalue is E1 [° ] and the half width of the peak is E2 [°]. The degree of2θ at which the peak F has the maximum value is F1 [° ] and the halfwidth of the peak is F2 [°].

A1 is preferably more than 16.82° and less than 17.52°, furtherpreferably more than 16.87° and less than 17.47°, still furtherpreferably more than 17.02° and less than 17.32°.

B1 is preferably more than 20.45° and less than 21.15°, furtherpreferably more than 20.50° and less than 21.10°, still furtherpreferably more than 20.65° and less than 20.95°.

C1 is preferably more than 25.24° and less than 25.94°, furtherpreferably more than 25.29° and less than 25.89°, still furtherpreferably more than 25.44° and less than 25.74°.

D1 is preferably more than 29.40° and less than 30.10°, furtherpreferably more than 29.45° and less than 30.05°, still furtherpreferably more than 29.60° and less than 29.90°.

E1 is preferably more than 31.90° and less than 32.60°, furtherpreferably more than 31.95° and less than 32.55°, still furtherpreferably more than 32.1° and less than 32.4°.

F1 is preferably more than 35.28° and less than 35.985°, furtherpreferably more than 35.33° and less than 35.93°, still furtherpreferably more than 35.48° and less than 35.78°.

The half width of the peak observed in the XRD measurement can be smallin some cases when the crystallinity is high. Further, the half width ofthe peak can be small when the grain size of the crystal is large. Thus,the half width of the peak observed in the XRD measurement is preferablyless than 2, further preferably less than 1, still further preferablyless than 0.3, still yet further preferably less than 0.2. For example,A2, B2, C2, D2, E2, and F2 are more than 0.02 and less than 2, more than0.03 and less than 2, or more than 0.03 and less than 1.

<Effect of pH>

Although the details are described in Example 1 later, the XRDmeasurement results of the product obtained after Step S211 in the casewhere the mixed solution B has a pH in the vicinity of 6 and the mixedsolution C has a pH in the vicinity of 5 are shown in FIG. 29A.

The XRD measurement results of the product obtained after Step S211 inthe case where the mixed solution B has a pH in the vicinity of 10 andthe mixed solution C has a pH in the vicinity of 9 are shown in FIG.28B. Although the details are described in Example 1 later, it issuggested that the XRD measurement results correspond to the peaks ofLi₃PO₄. In Step S207, Li₃PO₄ used for manufacturing the mixed solutionprobably remains. Further, the peak observed at 31.7° probablycorresponds to NH₄FePO₄.H₂O.

The XRD measurement results of the product obtained after Step S211 inthe case where the mixed solution B has a pH in the vicinity of 8 andthe mixed solution C has a pH in the vicinity of 6 are shown in FIG.28A. Although the details are described in Example 1 later, it issuggested that the XRD measurement results correspond to the peaks ofNH₄FePO₄.H₂O according to the database.

In such a manner, in the case where pH of the mixed solution B is high,for example, in the case where a pH exceeds 7, yield of the targetsynthetic material A decreases and compounds such as Li₃PO₄ andNH₄FePO₄.H₂O are generated in some cases.

The lithium-containing complex phosphate of one embodiment of thepresent invention can be used as an active material in a lithium ionbattery. The lithium-containing complex phosphate of one embodiment ofthe present invention preferably has an olivine structure. Further, inthe case where the lithium-containing complex phosphate of oneembodiment of the present invention has an olivine structure, thecapacity per unit weight of the active material is more than or equal to100 mAh/g and less than or equal to 170 mAh/g or more than or equal to130 mAh/g and less than or equal to 160 mAh/g in the case where the rateis 0.2 C, for example.

Embodiment 2

In this embodiment, a storage battery of one embodiment of the presentinvention will be described.

A storage battery of one embodiment of the present invention includes apositive electrode, a negative electrode, and an electrolytic solution.

The positive electrode active material preferably includes thelithium-containing complex phosphate and the like described inEmbodiment 1.

[Negative Electrode Active Material]

In the case where the active material is a negative electrode activematerial, for example, an alloy-based material, a carbon-based material,or the like can be used.

For the negative electrode active material, an element which enablescharge-discharge reactions by an alloying reaction and a dealloyingreaction with lithium can be used. For example, a material containing atleast one of silicon, tin, gallium, aluminum, germanium, lead, antimony,bismuth, silver, zinc, cadmium, indium, and the like can be used. Suchelements have higher capacity than carbon. In particular, silicon has ahigh theoretical capacity of 4200 mAh/g. For this reason, silicon ispreferably used as the negative electrode active material.Alternatively, a compound containing any of the above elements may beused. Examples of the compound include SiO, Mg₂Si, Mg₂Ge, SnO, SnO₂,Mg₂Sn, SnS₂, V₂Sn₃, FeSn₂, CoSn₂, Ni₃Sn₂, Cu₆Sn₅, Ag₃Sn, Ag₃Sb, Ni₂MnSb,CeSb₃, LaSn₃, La₃Co₂Sn₇, CoSb₃, InSb, SbSn, and the like. Here, anelement that enables charge-discharge reactions by an alloying reactionand a dealloying reaction with lithium, a compound containing theelement, and the like may be referred to as an alloy-based material.

In this specification and the like, SiO refers, for example, to siliconmonoxide. SiO can alternatively be expressed as SiOx. Here, x preferablyhas an approximate value of 1. For example, x is preferably 0.2 or moreand 1.5 or less, more preferably 0.3 or more and 1.2 or less.

As the carbon-based material, graphite, graphitizing carbon (softcarbon), non-graphitizing carbon (hard carbon), a carbon nanotube,graphene, carbon black, or the like can be used.

Examples of graphite include artificial graphite and natural graphite.Examples of artificial graphite include meso-carbon microbeads (MCMB),coke-based artificial graphite, and pitch-based artificial graphite. Asartificial graphite, spherical graphite having a spherical shape can beused. For example, MCMB is preferably used because it may have aspherical shape. Moreover, MCMB may preferably be used because it canrelatively easily have a small surface area. Examples of naturalgraphite include flake graphite and spherical natural graphite.

Graphite has a low potential substantially equal to that of a lithiummetal (higher than or equal to 0.05 V and lower than or equal to 0.3 Vvs. Li/Li⁺) when lithium ions are intercalated into the graphite (whilea lithium-graphite intercalation compound is generated). For thisreason, a lithium ion secondary battery can have a high operatingvoltage. In addition, graphite is preferred because of its advantagessuch as a relatively high capacity per unit volume, relatively smallvolume expansion, low cost, and higher level of safety than that of alithium metal.

Alternatively, for the negative electrode active materials, an oxidesuch as titanium dioxide (TiO₂), lithium titanium oxide (Li₄Ti₅O₁₂),lithium-graphite intercalation compound (Li_(x)C₆), niobium pentoxide(Nb₂O₅), tungsten oxide (WO₂), or molybdenum oxide (MoO₂) can be used.

Still alternatively, for the negative electrode active materials,Li_(3-x)M_(x)N (M=Co, Ni, or Cu) with a Li₃N structure, which is anitride containing lithium and a transition metal, can be used. Forexample, Li_(2.6)Co_(0.4)N₃ is preferable because of high charge anddischarge capacity (900 mAh/g and 1890 mAh/cm³).

A nitride containing lithium and a transition metal is preferably used,in which case lithium ions are contained in the negative electrodeactive materials and thus the negative electrode active materials can beused in combination with a material for a positive electrode activematerial which does not contain lithium ions, such as V₂O₅ or Cr₃O₈. Inthe case of using a material containing lithium ions as a positiveelectrode active material, the nitride containing lithium and atransition metal can be used for the negative electrode active materialby extracting the lithium ions contained in the positive electrodeactive material in advance.

Alternatively, a material which causes a conversion reaction can be usedfor the negative electrode active materials; for example, a transitionmetal oxide which does not form an alloy with lithium, such as cobaltoxide (CoO), nickel oxide (NiO), and iron oxide (FeO), may be used.Other examples of the material which causes a conversion reactioninclude oxides such as Fe₂O₃, CuO, Cu₂O, RuO₂, and Cr₂O₃, sulfides suchas CoS_(0.89), NiS, and CuS, nitrides such as Zn₃N₂, Cu₃N, and Ge₃N₄,phosphides such as NiP₂, FeP₂, and CoP₃, and fluorides such as FeF₃ andBiF₃.

[Predoping]

In the case where a coating film is formed in the initial charge anddischarge cycle, an irreversible reaction occurs. For example, in thecase where one of an irreversible reaction at the positive electrode andan irreversible reaction at the negative electrode is greater, thebalance between charge and discharge might be disrupted, resulting in adecrease in the capacity of the storage battery. Replacing an electrodeused as a counter electrode after charge and discharge using the counterelectrode are performed can inhibit a decrease in capacity. For example,charge or charge and discharge are performed using a positive electrodein combination with a negative electrode, and then, the positiveelectrode is removed to be replaced with another positive electrode inthe storage battery. This may inhibit a decrease in the capacity of thestorage battery. This method may be called predoping or preaging.

A current collector included in each of the positive electrode and thenegative electrode can be formed using a material that has highconductivity, such as a metal of stainless steel, gold, platinum,aluminum, titanium, or the like, or an alloy thereof. In the case wherethe current collector is used in the positive electrode, it is preferredthat it not dissolve at the potential of the positive electrode. In thecase where the current collector is used in the negative electrode, itis preferred that it not be alloyed with carrier ions such as lithium.Alternatively, the current collector can be formed using an aluminumalloy to which an element that improves heat resistance, such assilicon, titanium, neodymium, scandium, or molybdenum, is added. Stillalternatively, a metal element that forms silicide by reacting withsilicon can be used. Examples of the metal element that forms silicideby reacting with silicon include zirconium, titanium, hafnium, vanadium,niobium, tantalum, chromium, molybdenum, tungsten, cobalt, nickel, andthe like. The current collector can have any of various shapes includinga foil-like shape, a plate-like shape (sheet-like shape), a net-likeshape, a punching-metal shape, and an expanded-metal shape. The currentcollector preferably has a thickness of 5 μm to 30 μm inclusive.

The positive electrode and the negative electrode may include aconductive additive. Examples of the conductive additive include acarbon material, a metal material, and a conductive ceramic material.Alternatively, a fiber material may be used as the conductive additive.The content of the conductive additive in the active material layer ispreferably greater than or equal to 1 wt % and less than or equal to 10wt %, more preferably greater than or equal to 1 wt % and less than orequal to 5 wt %.

A network for electric conduction can be formed in the electrode by theconductive additive. The conductive additive also allows maintaining ofa path for electric conduction between the positive electrode activematerial particles. The addition of the conductive additive to theactive material layer increases the electric conductivity of the activematerial layer.

Examples of the conductive additive include natural graphite, artificialgraphite such as mesocarbon microbeads, and carbon fiber. Examples ofcarbon fiber include mesophase pitch-based carbon fiber, isotropicpitch-based carbon fiber, carbon nanofiber, and carbon nanotube. Carbonnanotube can be formed by, for example, a vapor deposition method. Otherexamples of the conductive additive include carbon materials such ascarbon black (e.g., acetylene black (AB)), graphite (black lead)particles, graphene, and fullerene. Alternatively, metal powder or metalfibers of copper, nickel, aluminum, silver, gold, or the like, aconductive ceramic material, or the like can be used.

Alternatively, a graphene compound may be used as the conductiveadditive.

A graphene compound may have excellent electrical characteristics ofhigh conductivity and excellent physical properties of high flexibilityand high mechanical strength. A graphene compound has a planar shape andenables low-resistant surface contact. Furthermore, a graphene compoundhas extremely high conductivity even with a small thickness in somecases and thus allows a conductive path to be formed in an activematerial layer efficiently even with a small amount. Thus, a graphenecompound is preferably used as a conductive additive, in which case thearea where an active material and the conductive additive are in contactwith each other can be increased and electrical resistance may bereduced. Here, it is particularly preferred that graphene, multilayergraphene, or reduced graphene oxide (hereinafter referred to as RGO) beused as a graphene compound. Note that RGO refers to a compound obtainedby reducing graphene oxide (GO), for example.

In the case where an active material with a small particle diameter(e.g., 1 μm or less) is used, the specific surface area of the activematerial is large and thus more conductive paths for the active materialparticles are needed. In such a case, a graphene compound that canefficiently form a conductive path even in a small amount isparticularly preferably used.

A cross-sectional structure example of the active material layercontaining a graphene compound as a conductive additive will bedescribed below.

FIG. 4A is a longitudinal sectional view of the active material layer.The active material layer includes active material particles 103,graphene compounds 321 as a conductive additive, and a binder (notillustrated). Here, graphene or multilayer graphene can be used as thegraphene compound 321, for example. The graphene compound 321 preferablyhas a sheet-like shape. The graphene compound 321 may have a sheet-likeshape formed of a plurality of sheets of multilayer graphene and/or aplurality of sheets of graphene that partly overlap with each other.

The longitudinal section of the active material layer in FIG. 4A showssubstantially uniform dispersion of the graphene compounds 321 in theactive material layer. The graphene compounds 321 are schematicallyshown by thick lines in FIG. 4A but are actually thin films each havinga thickness corresponding to the thickness of a single layer or amulti-layer of carbon molecules. The plurality of graphene compounds 321are formed in such a way as to wrap, coat, or adhere to the surfaces ofthe plurality of active material particles 103, so that the graphenecompounds 321 make surface contact with the active material particles103.

Here, a plurality of graphene compounds are bonded to each other to formnet-like graphene compound sheet (hereinafter referred to as a graphenecompound net or a graphene net). The graphene net covering the activematerial can function as a binder for binding active materials. Theamount of the binder can thus be reduced, or the binder does not have tobe used. This can increase the proportion of the active material in theelectrode volume or weight. That is to say, the capacity of the powerstorage device can be increased.

Here, it is preferable to perform reduction after a layer to be theactive material layer is formed in such a manner that graphene oxide isused as the graphene compound 321 and mixed with an active material.When graphene oxide with extremely high dispersibility in a polarsolvent is used for the formation of the graphene compounds 321, thegraphene compounds 321 can be substantially uniformly dispersed in theactive material layer. The solvent is removed by volatilization from adispersion medium in which graphene oxide is uniformly dispersed, andthe graphene oxide is reduced; hence, the graphene compounds 321remaining in the active material layer partly overlap with each otherand are dispersed such that surface contact is made, thereby forming athree-dimensional conduction path. Note that graphene oxide can bereduced either by heat treatment or with the use of a reducing agent,for example.

Unlike a conductive additive in the form of particles, such as acetyleneblack, which makes point contact with an active material, the graphenecompound 321 is capable of making low-resistance surface contact;accordingly, the electrical conduction between the active materialparticles 103 and the graphene compounds 321 can be improved with asmaller amount of the graphene compounds 321 than that of a normalconductive additive. Thus, the proportion of the active materialparticles 103 in the active material layer can be increased.Accordingly, the discharge capacity of a power storage device can beincreased.

The positive electrode and the negative electrode may each include abinder. As the binder, a rubber material such as styrene-butadienerubber (SBR), styrene-isoprene-styrene rubber, acrylonitrile-butadienerubber, butadiene rubber, or ethylene-propylene-diene copolymer can beused. Alternatively, fluororubber can be used as the binder.

For the binder, for example, water-soluble polymers are preferably used.As the water-soluble polymers, a polysaccharide or the like can be used.As the polysaccharide, a cellulose derivative such as carboxymethylcellulose (CMC), methyl cellulose, ethyl cellulose, hydroxypropylcellulose, diacetyl cellulose, or regenerated cellulose, starch, or thelike can be used. It is more preferred that such water-soluble polymersbe used in combination with any of the above rubber materials.

Alternatively, as the binder, a material such as polystyrene,poly(methyl acrylate), poly(methyl methacrylate) (PMMA), sodiumpolyacrylate, polyvinyl alcohol (PVA), polyethylene oxide (PEO),polypropylene oxide, polyimide, polyvinyl chloride,polytetrafluoroethylene, polyethylene, polypropylene, polyisobutylene,polyethylene terephthalate, nylon, polyvinylidene fluoride (PVdF),polyacrylonitrile (PAN), ethylene-propylene-diene polymer, polyvinylacetate, or nitrocellulose is preferably used.

Two or more of the above materials may be used in combination for thebinder.

For example, a material having a significant viscosity modifying effectand another material may be used in combination. For example, a rubbermaterial or the like has high adhesion or high elasticity but may havedifficulty in viscosity modification when mixed in a solvent. In such acase, a rubber material or the like is preferably mixed with a materialhaving a significant viscosity modifying effect, for example. As amaterial having a significant viscosity modifying effect, for example, awater-soluble polymer is preferably used. An example of a water-solublepolymer having an especially significant viscosity modifying effect isthe above-mentioned polysaccharide; for example, a cellulose derivativesuch as carboxymethyl cellulose (CMC), methyl cellulose, ethylcellulose, hydroxypropyl cellulose, diacetyl cellulose, or regeneratedcellulose, or starch can be used.

Note that a cellulose derivative such as carboxymethyl cellulose obtainsa higher solubility when converted into a salt such as a sodium salt oran ammonium salt of carboxymethyl cellulose, and accordingly, easilyexerts an effect as a viscosity modifier. The high solubility can alsoincrease the dispersibility of an active material and other componentsin the formation of slurry for an electrode. In this specification,cellulose and a cellulose derivative used as a binder of an electrodeinclude salts thereof.

The water-soluble polymers stabilize viscosity by being dissolved inwater and allow stable dispersion of the active material and anothermaterial combined as a binder such as styrene-butadiene rubber in anaqueous solution. Furthermore, a water-soluble polymer is expected to beeasily and stably adsorbed to an active material surface because it hasa functional group. Many cellulose derivatives such as carboxymethylcellulose have functional groups such as a hydroxyl group and a carboxylgroup. Because of functional groups, polymers are expected to interactwith each other and cover an active material surface in a large area.

In the case where the binder covering or being in contact with theactive material surface forms a film, the film is expected to serve as apassivation film to suppress the decomposition of the electrolyticsolution. Here, the passivation film refers to a film without electricconductivity or a film with extremely low electric conductivity, and caninhibit the decomposition of an electrolytic solution at a potential atwhich a battery reaction occurs in the case where the passivation filmis formed on the active material surface, for example. It is preferredthat the passivation film can conduct lithium ions while suppressingelectric conduction.

[Method for Manufacturing Electrode]

In examples of methods for manufacturing negative and positiveelectrodes, a slurry is formed and an electrode is manufactured byapplication of the slurry. A method for forming a slurry used formanufacturing an electrode will be described.

A polar solvent is preferably used as the solvent used for formation ofthe slurry. Examples of the polar solvent include water, methanol,ethanol, acetone, tetrahydrofuran (THF), dimethylformamide (DMF),N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), and a mixedsolution of any two or more of the above.

First, the active material, the conductive additive, and the binder aremixed to form Mixture A (Step S110). Next, the solvent is added toMixture A and kneading (mixing with a high viscosity) is performed, sothat Mixture B is formed (Step S120). Here, Mixture B is preferably in apaste form, for example. In the case where a second binder is added in alater step S141, a first binder is not necessarily added in Step S110 insome cases.

Next, the solvent is added to Mixture B and kneading is performed, sothat Mixture C is formed (Step S130).

Next, in the case where the second binder is used, the second binder isadded to form Mixture D (Step S141). At this time, a solvent may beadded. In the case where the second binder is not used, a solvent isadded as needed to form Mixture E (Step S142).

Then, Mixture D or Mixture E is mixed in a reduced-pressure atmosphereto form Mixture F (Step S150). At this time, a solvent may be added. Inthe mixing and kneading steps in Steps S110 to S150, a mixer may beused, for example.

Next, the viscosity of Mixture F is measured (Step S160). After that, asolvent is added as needed to adjust the viscosity. Through the abovesteps, slurry for application of the active material layer is obtained.

Here, for example, the higher the viscosity of Mixtures C to F in StepsS130 to S160 is, the higher the dispersibility of the active material,the binder, and the conductive additive in the mixtures is (the betterthey are mixed together), in some cases. Thus, the viscosity F ispreferably higher. However, an excessively high viscosity of Mixture Fis not preferred in terms of productivity because it might reduce theelectrode application speed.

Next, a method for manufacturing the active material layer over thecurrent collector with the use of the formed slurry will be described.

First, the slurry is applied to the current collector. Before theapplication of the slurry, surface treatment may be performed on thecurrent collector. Examples of surface treatment include coronadischarge treatment, plasma treatment, and undercoat treatment. Here,the “undercoat” refers to a film formed over a current collector beforeapplication of slurry onto the current collector for the purpose ofreducing the interface resistance between an active material layer andthe current collector or increasing the adhesion between the activematerial layer and the current collector. Note that the undercoat is notnecessarily formed in a film shape, and may be formed in an islandshape. In addition, the undercoat may serve as an active material tohave capacity. For the undercoat, a carbon material can be used, forexample. Examples of the carbon material include graphite, carbon blacksuch as acetylene black and ketjen black (registered trademark), and acarbon nanotube.

For the application of the slurry, a slot die method, a gravure method,a blade method, or combination of any of them can be used. Furthermore,a continuous coater or the like may be used for the application.

Then, the solvent of the slurry is volatilized to form the activematerial layer.

The step of volatilizing the solvent of the slurry is preferablyperformed at a temperature in the range from 50° C. to 200° C.inclusive, more preferably from 60° C. to 150° C. inclusive.

Heat treatment is performed using a hot plate at 30° C. or higher and70° C. or lower in an air atmosphere for longer than or equal to 10minutes, and then, for example, another heat treatment is performed atroom temperature or higher and 100° C. or lower in a reduced-pressureenvironment for longer than or equal to 1 hour and shorter than or equalto 10 hours.

Alternatively, heat treatment may be performed using a drying furnace orthe like. In the case of using a drying furnace, the heat treatment isperformed at 30° C. or higher and 120° C. or lower for longer than orequal to 30 seconds and shorter than or equal to 20 minutes, forexample.

The temperature may be increased in stages. For example, after heattreatment is performed at 60° C. or lower for shorter than or equal to10 minutes, another heat treatment may further be performed at higherthan or equal to 65° C. for longer than or equal to 1 minute.

The thickness of the active material layer formed through the abovesteps is, for example, preferably greater than or equal to 5 μm and lessthan or equal to 300 μm, more preferably greater than or equal to 10 μmand less than or equal to 150 μm. Furthermore, the amount of the activematerial in the active material layer is, for example, preferablygreater than or equal to 2 mg/cm² and less than or equal to 50 mg/cm².

The active material layer may be formed over only one surface of thecurrent collector, or the active material layers may be formed such thatthe current collector is sandwiched therebetween. Alternatively, theactive material layers may be formed such that part of the currentcollector is sandwiched therebetween.

After the volatilization of the solvent from the active material layer,pressing may be performed by a compression method such as a roll pressmethod or a flat plate press method. In performing pressing, heat may beapplied.

Note that the active material layer may be predoped. There is noparticular limitation on the method for predoping the active materiallayer. For example, the active material layer may be predopedelectrochemically. For example, before a battery is assembled, theactive material layer can be predoped with lithium in an electrolyticsolution described later with the use of a lithium metal as a counterelectrode. Alternatively, predoping may be performed using a positiveelectrode for predoping as a counter electrode of a negative electrode,and then, the positive electrode for predoping may be removed. Predopingcan particularly inhibit a decrease in initial charge and dischargeefficiency, leading to an increase in the capacity of the storagebattery.

This embodiment can be implemented in combination with any of the otherembodiments as appropriate.

Embodiment 3

In this embodiment, power storage devices of embodiments of the presentinvention will be described.

Examples of the power storage device of one embodiment of the presentinvention include a secondary battery that utilizes an electrochemicalreaction, such as a lithium ion battery, an electrochemical capacitorsuch as an electric double-layer capacitor or a redox capacitor, an airbattery, and a fuel battery.

<Thin Storage Battery>

FIG. 5 illustrates a thin storage battery as an example of a storagedevice. When a flexible thin storage battery is used in an electronicdevice at least part of which is flexible, the storage battery can bebent as the electronic device is bent.

FIG. 5 is an external view of a storage battery 500, which is a thinstorage battery. FIG. 6A is a cross-sectional view along dashed-dottedline A1-A2 in FIG. 5, and FIG. 6B is a cross-sectional view alongdashed-dotted line B1-B2 in FIG. 5. The storage battery 500 includes apositive electrode 503 including a positive electrode current collector501 and a positive electrode active material layer 502, a negativeelectrode 506 including a negative electrode current collector 504 and anegative electrode active material layer 505, a separator 507, anelectrolytic solution 508, and an exterior body 509. The separator 507is provided between the positive electrode 503 and the negativeelectrode 506 in the exterior body 509. The electrolytic solution 508 iscontained in the exterior body 509.

As a solvent of the electrolytic solution 508, an aprotic organicsolvent is preferably used. For example, one of ethylene carbonate (EC),propylene carbonate (PC), butylene carbonate, chloroethylene carbonate,vinylene carbonate, γ-butyrolactone, γ-valerolactone, dimethyl carbonate(DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), methylformate, methyl acetate, methyl butyrate, 1,3-dioxane, 1,4-dioxane,dimethoxyethane (DME), dimethyl sulfoxide, diethyl ether, methyldiglyme, acetonitrile, benzonitrile, tetrahydrofuran, sulfolane, andsultone can be used, or two or more of these solvents can be used in anappropriate combination in an appropriate ratio.

When a gelled high-molecular material is used as the solvent of theelectrolytic solution, safety against liquid leakage and the like isimproved. Furthermore, a secondary battery can be thinner and morelightweight. Typical examples of gelled high-molecular materials includea silicone gel, an acrylic gel, an acrylonitrile gel, a polyethyleneoxide-based gel, a polypropylene oxide-based gel, a gel of afluorine-based polymer, and the like.

Alternatively, the use of one or more types of ionic liquids (roomtemperature molten salts) which have features of non-flammability andnon-volatility as a solvent of the electrolytic solution can prevent apower storage device from exploding or catching fire even when a powerstorage device internally shorts out or the internal temperatureincreases owing to overcharging or the like. An ionic liquid contains acation and an anion. The ionic liquid contains an organic cation and ananion. Examples of the organic cation used for the electrolytic solutioninclude aliphatic onium cations such as a quaternary ammonium cation, atertiary sulfonium cation, and a quaternary phosphonium cation, andaromatic cations such as an imidazolium cation and a pyridinium cation.Examples of the anion used for the electrolyte solution include amonovalent amide-based anion, a monovalent methide-based anion, afluorosulfonate anion, a perfluoroalkylsulfonate anion, atetrafluoroborate anion, a perfluoroalkylborate anion, ahexafluorophosphate anion, and a perfluoroalkylphosphate anion.

In the case of using lithium ions as carriers, as an electrolytedissolved in the above-described solvent, one of lithium salts such asLiPF₆, LiClO₄, LiAsF₆, LiBF₄, LiAlCl₄, LiSCN, LiBr, LiI, Li₂SO₄,Li₂B₁₀Cl₁₀, Li₂B₁₂Cl₁₂, LiCF₃SO₃, LiC₄F₉SO₃, LiC(CF₃SO₂)₃,LiC(C₂F₅SO₂)₃, LiN(CF₃SO₂)₂, LiN(C₄F₉SO₂) (CF₃SO₂), and LiN(C₂F₅SO₂)₂can be used, or two or more of these lithium salts can be used in anappropriate combination in an appropriate ratio.

The electrolytic solution used for a power storage device is preferablyhighly purified and contains a small amount of dust particles andelements other than the constituent elements of the electrolyticsolution (hereinafter, also simply referred to as impurities).Specifically, the weight ratio of impurities to the electrolyticsolution is less than or equal to 1%, preferably less than or equal to0.1%, and more preferably less than or equal to 0.01%.

Furthermore, an additive agent such as vinylene carbonate, propanesultone (PS), tert-butylbenzene (TBB), fluoroethylene carbonate (FEC),or LiBOB may be added to the electrolytic solution. The concentration ofsuch an additive agent in the whole solvent is, for example, higher thanor equal to 0.1 wt % and lower than or equal to 5 wt %.

Alternatively, a gel polymer electrolyte obtained in such a manner thata polymer is swelled with an electrolytic solution may be used.

Examples of polymers include a polymer having a polyalkylene oxidestructure, such as polyethylene oxide (PEO); PVDF; polyacrylonitrile;and a copolymer containing any of them. For example, PVDF-HFP, which isa copolymer of PVDF and hexafluoropropylene (HFP) can be used. Theformed polymer may be porous.

Instead of the electrolytic solution, a solid electrolyte including aninorganic material such as a sulfide-based inorganic material or anoxide-based inorganic material, or a solid electrolyte including ahigh-molecular material such as a polyethylene oxide (PEO)-basedhigh-molecular material may alternatively be used. When the solidelectrolyte is used, a separator and a spacer are not necessary.Furthermore, the battery can be entirely solidified; therefore, there isno possibility of liquid leakage and thus the safety of the battery isdramatically increased.

As the separator 507, paper; nonwoven fabric; glass fiber; ceramics;synthetic fiber containing nylon (polyamide), vinylon (polyvinylalcohol-based fiber), polyester, acrylic, polyolefin, or polyurethane;or the like can be used.

The separator 507 is preferably formed to have a bag-like shape tosurround one of the positive electrode 503 and the negative electrode506. For example, as illustrated in FIG. 7A, the separator 507 is foldedin two so that the positive electrode 503 is sandwiched, and sealed witha sealing member 514 in a region outside the region overlapping with thepositive electrode 503; thus, the positive electrode 503 can be reliablysupported inside the separator 507. Then, as illustrated in FIG. 7B, thepositive electrodes 503 surrounded by the separators 507 and thenegative electrodes 506 are alternately stacked and provided in theexterior body 509, whereby the storage battery 500 can be formed.

Next, aging after manufacturing a storage battery will be described.Aging is preferably performed after fabrication of a storage battery.The aging can be performed under the following conditions, for example.Charge is performed at a rate of 0.001 C or more and 0.2 C or less at atemperature higher than or equal to room temperature and lower than orequal to 50° C. In the case where the reaction potential of the positiveelectrode or the negative electrode is out of the range of the potentialwindow of the electrolytic solution 508, the electrolytic solution isdecomposed by charge and discharge operations of a storage battery insome cases. In the case where the electrolytic solution is decomposedand a gas is generated and accumulated in the cell, the electrolyticsolution cannot be in contact with a surface of the electrode in someregions. That is to say, an effectual reaction area of the electrode isreduced and effectual resistance is increased.

When the resistance is extremely increased, the negative electrodepotential is lowered. Consequently, lithium is intercalated intographite and lithium is deposited on the surface of graphite. Thelithium deposition might reduce capacity. For example, if a film or thelike is grown on the surface after lithium deposition, lithium depositedon the surface cannot be dissolved again. This lithium cannot contributeto capacity. In addition, when deposited lithium is physically collapsedand conduction with the electrode is lost, the lithium also cannotcontribute to capacity. Therefore, the gas is preferably released beforethe negative electrode potential reaches the potential of lithiumbecause of an increase in a charging voltage.

After the release of the gas, the charging state may be maintained at atemperature higher than room temperature, preferably higher than orequal to 30° C. and lower than or equal to 60° C., more preferablyhigher than or equal to 35° C. and lower than or equal to 50° C. for,for example, 1 hour or more and 100 hours or less. In the initialcharge, an electrolytic solution decomposed on the surface forms a filmon a surface of graphite. The formed coating film may thus be densifiedwhen the charging state is held at a temperature higher than roomtemperature after the release of the gas, for example.

FIGS. 8A and 8B illustrate an example where current collectors arewelded to a lead electrode. As illustrated in FIG. 8A, the positiveelectrodes 503 each wrapped by the separator 507 and the negativeelectrodes 506 are alternately stacked. Then, the positive electrodecurrent collectors 501 are welded to a positive electrode lead electrode510, and the negative electrode current collectors 504 are welded to anegative electrode lead electrode 511. FIG. 8B illustrates an example inwhich the positive electrode current collectors 501 are welded to thepositive electrode lead electrode 510. The positive electrode currentcollectors 501 are welded to the positive electrode lead electrode 510in a welding region 512 by ultrasonic welding or the like. The positiveelectrode current collector 501 includes a bent portion 513 asillustrated in FIG. 8B, and it is therefore possible to relieve stressdue to external force applied after manufacturing the storage battery500. The reliability of the storage battery 500 can be thus increased.

In the storage battery 500 illustrated in FIG. 5 and FIGS. 6A and 6B,the positive electrode current collectors 501 in the positive electrode503 and the negative electrode current collectors 504 in the negativeelectrode 506 are welded to the positive electrode lead electrode 510and a negative electrode lead electrode 511, respectively, by ultrasonicwelding. The positive electrode current collector 501 and the negativeelectrode current collector 504 can double as terminals for electricalcontact with the outside. In that case, the positive electrode currentcollector 501 and the negative electrode current collector 504 may bearranged so that part of the positive electrode current collector 501and part of the negative electrode current collector 504 are exposed tothe outside of the exterior body 509 without using lead electrodes.

Although the positive electrode lead electrode 510 and the negativeelectrode lead electrode 511 are provided on the same side in FIG. 5,the positive electrode lead electrode 510 and the negative electrodelead electrode 511 may be provided on different sides as illustrated inFIG. 9. The lead electrodes of a storage battery of one embodiment ofthe present invention can be freely positioned as described above;therefore, the degree of freedom in design is high. Accordingly, aproduct including a storage battery of one embodiment of the presentinvention can have a high degree of freedom in design. Furthermore, ayield of products each including a storage battery of one embodiment ofthe present invention can be increased.

As the exterior body 509 in the storage battery 500, for example, a filmhaving a three-layer structure in which a highly flexible metal thinfilm of aluminum, stainless steel, copper, nickel, or the like isprovided over a film formed of a material such as polyethylene,polypropylene, polycarbonate, ionomer, or polyamide, and an insulatingsynthetic resin film of a polyamide-based resin, a polyester-basedresin, or the like is provided as the outer surface of the exterior bodyover the metal thin film can be used.

Although the examples in FIGS. 6A and 6B each include five positiveelectrode active material layer-negative electrode active material layerpairs (the positive and negative electrode active material layers ofeach pair face each other), it is needless to say that the number ofpairs of electrode active material layers is not limited to five, andmay be more than five or less than five. In the case of using a largenumber of active material layers, the storage battery can have a highcapacity. In contrast, in the case of using a small number of activematerial layers, the storage battery can have a small thickness and highflexibility.

In the above structure, the exterior body 509 of the storage battery canchange its form such that the smallest curvature radius is greater thanor equal to 3 mm and less than or equal to 30 mm, preferably greaterthan or equal to 3 mm and less than or equal to 10 mm. One or two filmsare used as the exterior body of the secondary battery. In the case of astorage battery having a layered structure, a cross-sectional structureof the battery that is bent is surrounded by two curves of the filmserving as the exterior body.

Description will be given of the radius of curvature of a surface withreference to FIGS. 10A to 10C. In FIG. 10A, on a plane 1701 along whicha curved surface 1700 is cut, part of a curve 1702 of the curved surface1700 is approximate to an arc of a circle, and the radius of the circleis referred to as a radius 1703 of curvature and the center of thecircle is referred to as a center 1704 of curvature. FIG. 10B is a topview of the curved surface 1700. FIG. 10C is a cross-sectional view ofthe curved surface 1700 taken along the plane 1701. When a curvedsurface is cut by a plane, the radius of curvature of a curve in a crosssection differs depending on the angle between the curved surface andthe plane or on the cut position, and the smallest radius of curvatureis defined as the radius of curvature of a surface in this specificationand the like.

In the case of bending a secondary battery in which a component 1805including electrodes, an electrolytic solution, and the like issandwiched between two films as exterior bodies, a radius 1802 ofcurvature of a film 1801 close to a center 1800 of curvature of thesecondary battery is smaller than a radius 1804 of curvature of a film1803 far from the center 1800 of curvature (FIG. 11A). When thesecondary battery is curved and has an arc-shaped cross section,compressive stress is applied to a surface of the film on the sidecloser to the center 1800 of curvature and tensile stress is applied toa surface of the film on the side further from the center 1800 ofcurvature (FIG. 11B). However, by forming a pattern includingprojections or depressions on surfaces of the exterior bodies, theinfluence of a strain can be reduced to be acceptable even whencompressive stress and tensile stress are applied. For this reason, thesecondary battery can change its form such that the exterior body on theside closer to the center of curvature has the smallest curvature radiusgreater than or equal to 3 mm and less than or equal to 30 mm,preferably greater than or equal to 3 mm and less than or equal to 10mm.

Note that the cross-sectional shape of the secondary battery is notlimited to a simple arc shape, and the cross section can be partlyarc-shaped; for example, a shape illustrated in FIG. 11C, a wavy shapeillustrated in FIG. 11D, or an S shape can be used. When the curvedsurface of the secondary battery has a shape with a plurality of centersof curvature, the secondary battery can change its form such that acurved surface with the smallest radius of curvature among radii ofcurvature with respect to the plurality of centers of curvature, whichis a surface of the exterior body on the side closer to the center ofcurvature, has the smallest curvature radius, for example, greater thanor equal to 3 mm and less than or equal to 30 mm, preferably greaterthan or equal to 3 mm and less than or equal to 10 mm.

Next, a variety of examples of the stack of the positive electrode, thenegative electrode, and the separator will be described.

FIG. 14A illustrates an example where six positive electrodes 111 andsix negative electrodes 115 are stacked. One surface of a positiveelectrode current collector 121 included in a positive electrode 111 isprovided with a positive electrode active material layer 122. Onesurface of a negative electrode current collector 125 included in anegative electrode 115 is provided with a negative electrode activematerial layer 126.

In the structure illustrated in FIG. 14A, the positive electrodes 111and the negative electrodes 115 are stacked so that surfaces of thepositive electrodes 111 on each of which the positive electrode activematerial layer 122 is not provided are in contact with each other andthat surfaces of the negative electrodes 115 on each of which thenegative electrode active material layer 126 is not provided are incontact with each other. When the positive electrodes 111 and thenegative electrodes 115 are stacked in this manner, contact surfacesbetween metals can be formed; specifically, the surfaces of the positiveelectrodes 111 on each of which the positive electrode active materiallayer 122 is not provided can be in contact with each other, and thesurfaces of the negative electrodes 115 on each of which the negativeelectrode active material layer 126 is not provided can be in contactwith each other. The coefficient of friction of the contact surfacebetween metals can be lower than that of a contact surface between theactive material and the separator.

Therefore, when the storage battery 500 is curved, the surfaces of thepositive electrodes 111 on each of which the positive electrode activematerial layer 122 is not provided slide on each other, and the surfacesof the negative electrodes 115 on each of which the negative electrodeactive material layer 126 is not provided slide on each other; thus, thestress due to the difference between the inner diameter and the outerdiameter of a curved portion can be relieved. Here, the inner diameterof the curved portion refers to the radius of curvature of the innersurface of the curved portion in the exterior body 509 of the storagebattery 500 in the case where the storage battery 500 is curved, forexample. Therefore, the deterioration of the storage battery 500 can beinhibited. Furthermore, the storage battery 500 can have highreliability.

FIG. 14B illustrates an example of a stack of the positive electrodes111 and the negative electrodes 115 which is different from that in FIG.14A. The structure illustrated in FIG. 14B is different from that inFIG. 14A in that the positive electrode active material layers 122 areprovided on both surfaces of the positive electrode current collector121. When the positive electrode active material layers 122 are providedon both the surfaces of the positive electrode current collector 121 asillustrated in FIG. 14B, the capacity per unit volume of the storagebattery 500 can be increased.

FIG. 14C illustrates an example of a stack of the positive electrodes111 and the negative electrodes 115 which is different from that in FIG.14B. The structure illustrated in FIG. 14C is different from that inFIG. 14B in that the negative electrode active material layers 126 areprovided on both surfaces of the negative electrode current collector125. When the negative electrode active material layers 126 are providedon both the surfaces of the negative electrode current collector 125 asillustrated in FIG. 14C, the capacity per unit volume of the storagebattery 500 can be further increased.

In the structures illustrated in FIGS. 14A to 14C, a separator 123 has abag-like shape by which the positive electrodes 111 are surrounded;however, one embodiment of the present invention is not limited thereto.FIG. 15A illustrates an example in which the separator 123 has adifferent structure from that in FIG. 14A. The structure illustrated inFIG. 15A is different from that in FIG. 14A in that the separator 123,which is sheet-like, is provided between every pair of the positiveelectrode active material layer 122 and the negative electrode activematerial layer 126. In the structure illustrated in FIG. 15A, sixpositive electrodes 111 and six negative electrodes 115 are stacked, andsix separators 123 are provided.

FIG. 15B illustrates an example in which the separator 123 differentfrom that in FIG. 15A is provided. The structure illustrated in FIG. 15Bis different from that in FIG. 15A in that one sheet of separator 123 isfolded more than once to be interposed between every pair of thepositive electrode active material layer 122 and the negative electrodeactive material layer 126. It can be said that the structure illustratedin FIG. 15B is a structure in which the separators 123 in the respectivelayers which are illustrated in FIG. 15A are extended and connectedtogether between the layers. In the structure of FIG. 15B, six positiveelectrodes 111 and six negative electrodes 115 are stacked and thus theseparator 123 needs to be folded at least five times. The separator 123is not necessarily provided so as to be interposed between every pair ofthe positive electrode active material layer 122 and the negativeelectrode active material layer 126, and the plurality of positiveelectrodes 111 and the plurality of negative electrodes 115 may be boundtogether by extending the separator 123.

Note that the positive electrode, the negative electrode, and theseparator may be stacked as illustrated in FIGS. 16A to 16C. FIG. 16A isa cross-sectional view of a first electrode assembly 130, and FIG. 16Bis a cross-sectional view of a second electrode assembly 131. FIG. 16Cis a cross-sectional view taken along the dashed-dotted line A1-A2 inFIG. 5. In FIG. 16C, the first electrode assembly 130, the secondelectrode assembly 131, and the separator 123 are selectivelyillustrated for the sake of clarity.

As illustrated in FIG. 16C, the storage battery 500 includes a pluralityof first electrode assemblies 130 and a plurality of second electrodeassemblies 131.

As illustrated in FIG. 16A, in each of the first electrode assemblies130, a positive electrode 111 a including the positive electrode activematerial layers 122 on both surfaces of a positive electrode currentcollector 121, the separator 123, a negative electrode 115 a includingthe negative electrode active material layers 126 on both surfaces of anegative electrode current collector 125, the separator 123, and thepositive electrode 111 a including the positive electrode activematerial layers 122 on both surfaces of the positive electrode currentcollector 121 are stacked in this order. As illustrated in FIG. 16B, ineach of the second electrode assemblies 131, the negative electrode 115a including the negative electrode active material layers 126 on bothsurfaces of the negative electrode current collector 125, the separator123, the positive electrode 111 a including the positive electrodeactive material layers 122 on both surfaces of the positive electrodecurrent collector 121, the separator 123, and the negative electrode 115a including the negative electrode active material layers 126 on bothsurfaces of the negative electrode current collector 125 are stacked inthis order.

As illustrated in FIG. 16C, the plurality of first electrode assemblies130 and the plurality of second electrode assemblies 131 are coveredwith the wound separator 123.

[Coin-Type Storage Battery]

Next, an example of a coin-type storage battery will be described as anexample of a power storage device with reference to FIGS. 12A and 12B.FIG. 12A is an external view of a coin-type (single-layer flat type)storage battery, and FIG. 12B is a cross-sectional view thereof.

In a coin-type storage battery 300, a positive electrode can 301doubling as a positive electrode terminal and a negative electrode can302 doubling as a negative electrode terminal are insulated from eachother and sealed by a gasket 303 made of polypropylene or the like. Apositive electrode 304 includes a positive electrode current collector305 and a positive electrode active material layer 306 provided incontact with the positive electrode current collector 305.

A negative electrode 307 includes a negative electrode current collector308 and a negative electrode active material layer 309 provided incontact with the negative electrode current collector 308.

The description of the positive electrode 503 can be referred to for thepositive electrode 304. The description of the positive electrode activematerial layer 502 can be referred to for the positive electrode activematerial layer 306. The description of the negative electrode 506 can bereferred to for the negative electrode 307. The description of thenegative electrode active material layer 505 can be referred to for thenegative electrode active material layer 309. The description of theseparator 507 can be referred to for a separator 310. The description ofthe electrolytic solution 508 can be referred to for the electrolyticsolution.

Note that only one surface of each of the positive electrode 304 and thenegative electrode 307 used for the coin-type storage battery 300 isprovided with an active material layer.

For the positive electrode can 301 and the negative electrode can 302, ametal having a corrosion-resistant property to an electrolytic solution,such as nickel, aluminum, or titanium, an alloy of such a metal, or analloy of such a metal and another metal (e.g., stainless steel or thelike) can be used. Alternatively, the positive electrode can 301 and thenegative electrode can 302 are preferably covered with nickel, aluminum,or the like in order to prevent corrosion due to the electrolyticsolution. The positive electrode can 301 and the negative electrode can302 are electrically connected to the positive electrode 304 and thenegative electrode 307, respectively.

The negative electrode 307, the positive electrode 304, and theseparator 310 are immersed in the electrolytic solution. Then, asillustrated in FIG. 12B, the positive electrode 304, the separator 310,the negative electrode 307, and the negative electrode can 302 arestacked in this order with the positive electrode can 301 positioned atthe bottom, and the positive electrode can 301 and the negativeelectrode can 302 are subjected to pressure bonding with the gasket 303interposed therebetween. In such a manner, the coin-type storage battery300 can be manufactured.

[Cylindrical Storage Battery]

Next, an example of a cylindrical storage battery will be described asan example of a power storage device with reference to FIGS. 13A and13B. As illustrated in FIG. 13A, a cylindrical storage battery 600includes a positive electrode cap (battery cap) 601 on the top surfaceand a battery can (outer can) 602 on the side surface and bottomsurface. The positive electrode cap 601 and the battery can 602 areinsulated from each other by a gasket (insulating gasket) 610.

FIG. 13B is a diagram schematically illustrating a cross section of thecylindrical storage battery. Inside the battery can 602 having a hollowcylindrical shape, a battery element in which a strip-like positiveelectrode 604 and a strip-like negative electrode 606 are wound with aseparator 605 interposed therebetween is provided. Although notillustrated, the battery element is wound around a center pin. One endof the battery can 602 is closed and the other end thereof is open. Forthe battery can 602, a metal having a corrosion-resistant property to anelectrolytic solution, such as nickel, aluminum, or titanium, an alloyof such a metal, or an alloy of such a metal and another metal (e.g.,stainless steel or the like) can be used. Alternatively, the battery can602 is preferably covered with nickel, aluminum, or the like in order toprevent corrosion due to the electrolytic solution. Inside the batterycan 602, the battery element in which the positive electrode, thenegative electrode, and the separator are wound is provided between apair of insulating plates 608 and 609 which face each other.Furthermore, a nonaqueous electrolytic solution (not illustrated) isinjected inside the battery can 602 provided with the battery element.As the nonaqueous electrolytic solution, a nonaqueous electrolyticsolution that is similar to those of the coin-type storage battery canbe used.

The description of the positive electrode 503 can be referred to for thepositive electrode 604. The description of the negative electrode 506can be referred to for the negative electrode 606. The description ofthe method for fabricating an electrode that is described in Embodiment2 can be referred to for the positive electrode 604 and the negativeelectrode 606. Since the positive electrode and the negative electrodeof the cylindrical storage battery are wound, active materials arepreferably formed on both sides of the current collectors. A positiveelectrode terminal (positive electrode current collecting lead) 603 isconnected to the positive electrode 604, and a negative electrodeterminal (negative electrode current collecting lead) 607 is connectedto the negative electrode 606. Both the positive electrode terminal 603and the negative electrode terminal 607 can be formed using a metalmaterial such as aluminum. The positive electrode terminal 603 and thenegative electrode terminal 607 are resistance-welded to a safety valvemechanism 612 and the bottom of the battery can 602, respectively. Thesafety valve mechanism 612 is electrically connected to the positiveelectrode cap 601 through a positive temperature coefficient (PTC)element 611. The safety valve mechanism 612 cuts off electricalconnection between the positive electrode cap 601 and the positiveelectrode 604 when the internal pressure of the battery exceeds apredetermined threshold value. The PTC element 611, which serves as athermally sensitive resistor whose resistance increases as temperaturerises, limits the amount of current by increasing the resistance, inorder to prevent abnormal heat generation. Note that barium titanate(BaTiO₃)-based semiconductor ceramic can be used for the PTC element.

In the case where an electrode is wound as in the cylindrical storagebattery illustrated in FIGS. 13A and 13B, a great stress is caused atthe time of winding the electrode. In addition, an outward stress froman axis of winding is applied to the electrode all the time in the casewhere a wound body of the electrode is provided in a housing. However,the active material can be prevented from being cleaved even when such agreat stress is applied to the electrode.

Note that in this embodiment, the coin-type storage battery, thecylindrical storage battery, and the thin storage battery are given asexamples of the storage battery; however, any of storage batteries witha variety of shapes, such as a sealed storage battery and a square-typestorage battery, can be used. Furthermore, a structure in which aplurality of positive electrodes, a plurality of negative electrodes,and a plurality of separators are stacked or wound may be employed. Forexample, FIGS. 17A to 17C to FIGS. 21A and 21B illustrate examples ofother storage batteries.

[Structural Example of Thin Storage Battery]

FIGS. 17A to 17C and FIGS. 18A to 18C illustrate structural examples ofthin storage batteries. A wound body 993 illustrated in FIG. 17Aincludes a negative electrode 994, a positive electrode 995, and aseparator 996.

The wound body 993 is obtained by winding a sheet of a stack in whichthe negative electrode 994 overlaps with the positive electrode 995 withthe separator 996 therebetween. The wound body 993 is covered with arectangular sealed container or the like; thus, a rectangular secondarybattery is fabricated.

Note that the number of stacks each including the negative electrode994, the positive electrode 995, and the separator 996 is determined asappropriate depending on capacity and element volume which are required.The negative electrode 994 is connected to a negative electrode currentcollector (not illustrated) via one of a lead electrode 997 and a leadelectrode 998. The positive electrode 995 is connected to a positiveelectrode current collector (not illustrated) via the other of the leadelectrode 997 and the lead electrode 998.

In a storage battery 990 illustrated in FIGS. 17B and 17C, the woundbody 993 is packed in a space formed by bonding a film 981 and a film982 having a depressed portion that serve as exterior bodies bythermocompression bonding or the like. The wound body 993 includes thelead electrode 997 and the lead electrode 998, and is soaked in anelectrolytic solution inside a space surrounded by the film 981 and thefilm 982 having a depressed portion.

For the film 981 and the film 982 having a depressed portion, a metalmaterial such as aluminum or a resin material can be used, for example.With the use of a resin material for the film 981 and the film 982having a depressed portion, the film 981 and the film 982 having adepressed portion can be changed in their forms when external force isapplied; thus, a flexible storage battery can be fabricated.

Although FIGS. 17B and 17C illustrate an example where a space is formedby two films, the wound body 993 may be placed in a space formed bybending one film.

Furthermore, in fabricating a flexible power storage device, a resinmaterial or the like can be used for an exterior body and a sealedcontainer of the power storage device. Note that in the case where aresin material is used for the exterior body and the sealed container, aconductive material is used for a portion connected to the outside.

For example, FIGS. 18B and 18C illustrate another example of a flexiblethin storage battery. The wound body 993 illustrated in FIG. 18A is thesame as that illustrated in FIG. 17A, and the detailed descriptionthereof is omitted.

In the storage battery 990 illustrated in FIGS. 18B and 18C, the woundbody 993 is packed in an exterior body 991. The wound body 993 includesthe lead electrode 997 and the lead electrode 998, and is soaked in anelectrolytic solution inside a space surrounded by the exterior body 991and an exterior body 992. For example, a metal material such as aluminumor a resin material can be used for the exterior bodies 991 and 992.With the use of a resin material for the exterior bodies 991 and 992,the exterior bodies 991 and 992 can be changed in their forms whenexternal force is applied; thus, a flexible thin storage battery can befabricated.

When the electrode including the active material of one embodiment ofthe present invention is used in the flexible thin storage battery, theactive material can be prevented from being cleaved even if a stresscaused by repeated bending of the thin storage battery is applied to theelectrode.

When the active material in which at least part of the cleavage plane iscovered with graphene is used for an electrode as described above, adecrease in the voltage and discharge capacity of a battery can beprevented. Accordingly, the charge-discharge cycle characteristics ofthe battery can be improved.

[Structural Example of Power Storage System]

Structural examples of power storage systems will be described withreference to FIGS. 19A and 19B to FIGS. 21A and 21B. Here, a powerstorage system refers to, for example, a device including a powerstorage device.

FIGS. 19A and 19B are external views of a power storage system. Thepower storage system includes a circuit board 900 and a storage battery913. A label 910 is attached to the storage battery 913. As shown inFIG. 19B, the power storage system further includes a terminal 951, aterminal 952, an antenna 914, and an antenna 915.

The circuit board 900 includes terminals 911 and a circuit 912. Theterminals 911 are connected to the terminals 951 and 952, the antennas914 and 915, and the circuit 912. Note that a plurality of terminals 911serving as a control signal input terminal, a power supply terminal, andthe like may be provided.

The circuit 912 may be provided on the rear surface of the circuit board900. The shape of each of the antennas 914 and 915 is not limited to acoil shape and may be a linear shape or a plate shape. Further, a planarantenna, an aperture antenna, a traveling-wave antenna, an EH antenna, amagnetic-field antenna, or a dielectric antenna may be used.Alternatively, the antenna 914 or the antenna 915 may be a flat-plateconductor. The flat-plate conductor can serve as one of conductors forelectric field coupling. That is, the antenna 914 or the antenna 915 canserve as one of two conductors of a capacitor. Thus, electric power canbe transmitted and received not only by an electromagnetic field or amagnetic field but also by an electric field.

The line width of the antenna 914 is preferably larger than that of theantenna 915. This makes it possible to increase the amount of electricpower received by the antenna 914.

The power storage system includes a layer 916 between the storagebattery 913 and the antennas 914 and 915. The layer 916 may have afunction of blocking an electromagnetic field by the storage battery913. As the layer 916, for example, a magnetic body can be used.

Note that the structure of the power storage system is not limited tothat shown in FIGS. 19A and 19B.

For example, as shown in FIGS. 20A1 and 20A2, two opposite surfaces ofthe storage battery 913 in FIGS. 19A and 19B may be provided withrespective antennas. FIG. 20A1 is an external view showing one side ofthe opposite surfaces, and FIG. 20A2 is an external view showing theother side of the opposite surfaces. For portions similar to those inFIGS. 19A and 19B, the description of the power storage systemillustrated in FIGS. 19A and 19B can be referred to as appropriate.

As illustrated in FIG. 20A1, the antenna 914 is provided on one of theopposite surfaces of the storage battery 913 with the layer 916interposed therebetween, and as illustrated in FIG. 20A2, the antenna915 is provided on the other of the opposite surfaces of the storagebattery 913 with a layer 917 interposed therebetween. The layer 917 hasa function of blocking an electromagnetic field by the storage battery913, for example. As the layer 917, for example, a magnetic body can beused.

With the above structure, both of the antennas 914 and 915 can beincreased in size.

Alternatively, as illustrated in FIGS. 20B1 and 20B2, two oppositesurfaces of the storage battery 913 in FIGS. 19A and 19B may be providedwith different types of antennas. FIG. 20B1 is an external view showingone side of the opposite surfaces, and FIG. 20B2 is an external viewshowing the other side of the opposite surfaces. For portions similar tothose in FIGS. 19A and 19B, the description of the power storage systemillustrated in FIGS. 19A and 19B can be referred to as appropriate.

As illustrated in FIG. 20B1, the antennas 914 and 915 are provided onone of the opposite surfaces of the storage battery 913 with the layer916 interposed therebetween, and as illustrated in FIG. 20B2, an antenna918 is provided on the other of the opposite surfaces of the storagebattery 913 with the layer 917 interposed therebetween. The antenna 918has a function of communicating data with an external device, forexample. An antenna with a shape that can be applied to the antennas 914and 915, for example, can be used as the antenna 918. As a system forcommunication using the antenna 918 between the power storage system andanother device, a response method that can be used between the powerstorage system and another device, such as NFC, can be employed.

Alternatively, as illustrated in FIG. 21A, the storage battery 913 inFIGS. 19A and 19B may be provided with a display device 920. The displaydevice 920 is electrically connected to the terminal 911 via a terminal919. It is possible that the label 910 is not provided in a portionwhere the display device 920 is provided. For portions similar to thosein FIGS. 19A and 19B, the description of the power storage systemillustrated in FIGS. 19A and 19B can be referred to as appropriate.

The display device 920 can display, for example, an image showingwhether charge is being carried out, an image showing the amount ofstored power, or the like. As the display device 920, electronic paper,a liquid crystal display device, an electroluminescent (EL) displaydevice, or the like can be used. For example, the use of electronicpaper can reduce power consumption of the display device 920.

Alternatively, as illustrated in FIG. 21B, the storage battery 913illustrated in FIGS. 19A and 19B may be provided with a sensor 921. Thesensor 921 is electrically connected to the terminal 911 via a terminal922. For portions similar to those in FIGS. 19A and 19B, the descriptionof the power storage system illustrated in FIGS. 19A and 19B can bereferred to as appropriate.

As the sensor 921, a sensor that has a function of measuring, forexample, force, displacement, position, speed, acceleration, angularvelocity, rotational frequency, distance, light, liquid, magnetism,temperature, chemical substance, sound, time, hardness, electric field,electric current, voltage, electric power, radiation, flow rate,humidity, gradient, oscillation, odor, or infrared rays can be used.With the sensor 921, for example, data on an environment (e.g.,temperature) where the power storage system is placed can be determinedand stored in a memory inside the circuit 912.

The electrode of one embodiment of the present invention is used in thestorage battery and the power storage system that are described in thisembodiment. The capacity of the storage battery and the power storagesystem can thus be high. Furthermore, energy density can be high.Moreover, reliability can be high, and life can be long.

This embodiment can be implemented in appropriate combination with anyof the other embodiments.

Embodiment 4

In this embodiment, an example of an electronic device including aflexible power storage device will be described.

FIGS. 22A to 22G illustrate examples of electronic devices including theflexible power storage devices described in Embodiment 3. Examples ofelectronic devices each including a flexible power storage deviceinclude television devices (also referred to as televisions ortelevision receivers), monitors of computers or the like, cameras suchas digital cameras and digital video cameras, digital photo frames,mobile phones (also referred to as mobile phones or mobile phonedevices), portable game machines, portable information terminals, audioreproducing devices, and large game machines such as pachinko machines.

In addition, a flexible power storage device can be incorporated along acurved inside/outside wall surface of a house or a building or a curvedinterior/exterior surface of a car.

FIG. 22A illustrates an example of a mobile phone. A mobile phone 7400is provided with a display portion 7402 incorporated in a housing 7401,an operation button 7403, an external connection port 7404, a speaker7405, a microphone 7406, and the like. Note that the mobile phone 7400includes a power storage device 7407.

FIG. 22B illustrates the mobile phone 7400 that is bent. When the wholemobile phone 7400 is bent by the external force, the power storagedevice 7407 included in the mobile phone 7400 is also bent. FIG. 22Cillustrates the bent power storage device 7407. The power storage device7407 is a thin storage battery. The power storage device 7407 is fixedin a state of being bent. Note that the power storage device 7407includes a lead electrode 7408 electrically connected to a currentcollector 7409. The current collector 7409 is, for example, copper foil,and partly alloyed with gallium; thus, adhesion between the currentcollector 7409 and an active material layer in contact with the currentcollector 7409 is improved and the power storage device 7407 can havehigh reliability even in a state of being bent.

FIG. 22D illustrates an example of a bangle display device. A portabledisplay device 7100 includes a housing 7101, a display portion 7102, anoperation button 7103, and a power storage device 7104. FIG. 22Eillustrates the bent power storage device 7104. When the display deviceis worn on a user's arm while the power storage device 7104 is bent, thehousing changes its form and the curvature of a part or the whole of thepower storage device 7104 is changed. Note that the radius of curvatureof a curve at a point refers to the radius of the circular arc that bestapproximates the curve at that point. The reciprocal of the radius ofcurvature is curvature. Specifically, a part or the whole of the housingor the main surface of the power storage device 7104 is changed in therange of radius of curvature from 40 mm to 150 mm inclusive. When theradius of curvature at the main surface of the power storage device 7104is greater than or equal to 40 mm and less than or equal to 150 mm, thereliability can be kept high.

FIG. 22F illustrates an example of a watch-type portable informationterminal. A portable information terminal 7200 includes a housing 7201,a display portion 7202, a band 7203, a buckle 7204, an operation button7205, an input output terminal 7206, and the like.

The portable information terminal 7200 is capable of executing a varietyof applications such as mobile phone calls, e-mailing, viewing andediting texts, music reproduction, Internet communication, and acomputer game.

The display surface of the display portion 7202 is curved, and imagescan be displayed on the curved display surface. In addition, the displayportion 7202 includes a touch sensor, and operation can be performed bytouching the screen with a finger, a stylus, or the like. For example,by touching an icon 7207 displayed on the display portion 7202,application can be started.

With the operation button 7205, a variety of functions such as timesetting, power on/off, on/off of wireless communication, setting andcancellation of a silent mode, and setting and cancellation of a powersaving mode can be performed. For example, the functions of theoperation button 7205 can be set freely by setting the operation systemincorporated in the portable information terminal 7200.

The portable information terminal 7200 can employ near fieldcommunication that is a communication method based on an existingcommunication standard. In that case, for example, mutual communicationbetween the portable information terminal 7200 and a headset capable ofwireless communication can be performed, and thus hands-free calling ispossible.

Moreover, the portable information terminal 7200 includes the inputoutput terminal 7206, and data can be directly transmitted to andreceived from another information terminal via a connector. In addition,charging via the input output terminal 7206 is possible. Note that thecharging operation may be performed by wireless power feeding withoutusing the input output terminal 7206.

The display portion 7202 of the portable information terminal 7200 isprovided with a power storage device including the electrode of oneembodiment of the present invention. For example, the power storagedevice 7104 illustrated in FIG. 22E that is in the state of being curvedcan be provided in the housing 7201. Alternatively, the power storagedevice 7104 illustrated in FIG. 22E can be provided in the band 7203such that it can be curved.

The portable information terminal 7200 preferably includes a sensor. Asthe sensor, for example a human body sensor such as a fingerprintsensor, a pulse sensor, or a temperature sensor, a touch sensor, apressure sensitive sensor, an acceleration sensor, or the like ispreferably mounted.

FIG. 22G illustrates an example of an armband display device. A displaydevice 7300 includes a display portion 7304 and the power storage deviceof one embodiment of the present invention. The display device 7300 caninclude a touch sensor in the display portion 7304 and can serve as aportable information terminal.

The display surface of the display portion 7304 is bent, and images canbe displayed on the bent display surface. A display state of the displaydevice 7300 can be changed by, for example, near field communication,which is a communication method based on an existing communicationstandard.

The display device 7300 includes an input output terminal, and data canbe directly transmitted to and received from another informationterminal via a connector. In addition, charging via the input outputterminal is possible. Note that the charging operation may be performedby wireless power feeding without using the input output terminal.

This embodiment can be combined with any of the other embodiments asappropriate.

Embodiment 5

In this embodiment, examples of electronic devices that can includepower storage devices will be described.

FIGS. 23A and 23B illustrate an example of a tablet terminal that can befolded in half. A tablet terminal 9600 illustrated in FIGS. 23A and 23Bincludes a housing 9630 a, a housing 9630 b, a movable portion 9640connecting the housings 9630 a and 9630 b, a display portion 9631including a display portion 9631 a and a display portion 9631 b, adisplay mode changing switch 9626, a power switch 9627, a power savingmode changing switch 9625, a fastener 9629, and an operation switch9628. FIG. 23A illustrates the tablet terminal 9600 that is opened, andFIG. 23B illustrates the tablet terminal 9600 that is closed.

The tablet terminal 9600 includes a power storage unit 9635 inside thehousings 9630 a and 9630 b. The power storage unit 9635 is providedacross the housings 9630 a and 9630 b, passing through the movableportion 9640.

Part of the display portion 9631 a can be a touch panel region 9632 a,and data can be input by touching operation keys 9638 that aredisplayed. Note that half of the area of the display portion 9631 a hasonly a display function and the other half of the area has a touch panelfunction. However, the structure of the display portion 9631 a is notlimited to this, and all the area of the display portion 9631 a may havea touch panel function. For example, all the area of the display portion9631 a can display a keyboard and serve as a touch panel while thedisplay portion 9631 b can be used as a display screen.

In the display portion 9631 b, as in the display portion 9631 a, part ofthe display portion 9631 b can be a touch panel region 9632 b. When akeyboard display switching button 9639 displayed on the touch panel istouched with a finger, a stylus, or the like, a keyboard can bedisplayed on the display portion 9631 b.

Touch input can be performed in the touch panel region 9632 a and thetouch panel region 9632 b at the same time.

The display mode changing switch 9626 allows switching between alandscape mode and a portrait mode, color display and black-and-whitedisplay, and the like. The power saving mode changing switch 9625 cancontrol display luminance in accordance with the amount of externallight in use of the tablet terminal 9600, which is measured with anoptical sensor incorporated in the tablet terminal 9600. In addition tothe optical sensor, other detecting devices such as sensors fordetermining inclination, such as a gyroscope sensor or an accelerationsensor, may be incorporated in the tablet terminal.

Although the display portion 9631 a and the display portion 9631 b havethe same display area in FIG. 23A, one embodiment of the presentinvention is not limited to this example. The display portion 9631 a andthe display portion 9631 b may have different display areas or differentdisplay quality. For example, one of the display portions 9631 a and9631 b may display higher definition images than the other.

The tablet terminal is closed in FIG. 23B. The tablet terminal includesa housing 9630, a solar cell 9633, and a charge and discharge controlcircuit 9634 including a DCDC converter 9636. The power storage unit ofone embodiment of the present invention is used as the power storageunit 9635.

The tablet terminal 9600 can be folded such that the housings 9630 a and9630 b overlap with each other when not in use. Thus, the displayportions 9631 a and 9631 b can be protected, which increases thedurability of the tablet terminal 9600. In addition, the power storageunit 9635 of one embodiment of the present invention has flexibility andcan be repeatedly bent without a significant decrease in charge anddischarge capacity. Thus, a highly reliable tablet terminal can beprovided.

The tablet terminal illustrated in FIGS. 23A and 23B can also have afunction of displaying various types of data (e.g., a still image, amoving image, and a text image), a function of displaying a calendar, adate, or the time on the display portion, a touch-input function ofoperating or editing data displayed on the display portion by touchinput, a function of controlling processing by various types of software(programs), and the like.

The solar cell 9633, which is attached on the surface of the tabletterminal, supplies electric power to a touch panel, a display portion,an image signal processing portion, and the like. Note that the solarcell 9633 can be provided on one or both surfaces of the housing 9630and the power storage unit 9635 can be charged efficiently. The use of alithium ion battery as the power storage unit 9635 brings an advantagesuch as reduction in size.

The structure and operation of the charge and discharge control circuit9634 illustrated in FIG. 23B will be described with reference to a blockdiagram in FIG. 23C. The solar cell 9633, the power storage unit 9635,the DCDC converter 9636, a converter 9637, switches SW1 to SW3, and thedisplay portion 9631 are illustrated in FIG. 23C, and the power storageunit 9635, the DCDC converter 9636, the converter 9637, and the switchesSW1 to SW3 correspond to the charge and discharge control circuit 9634in FIG. 23B.

First, an example of operation when electric power is generated by thesolar cell 9633 using external light will be described. The voltage ofelectric power generated by the solar cell is raised or lowered by theDCDC converter 9636 to a voltage for charging the power storage unit9635. When the display portion 9631 is operated with the electric powerfrom the solar cell 9633, the switch SW1 is turned on and the voltage ofthe electric power is raised or lowered by the converter 9637 to avoltage needed for operating the display portion 9631. When display onthe display portion 9631 is not performed, the switch SW1 is turned offand the switch SW2 is turned on, so that the power storage unit 9635 canbe charged.

Note that the solar cell 9633 is described as an example of a powergeneration means; however, one embodiment of the present invention isnot limited to this example. The power storage unit 9635 may be chargedusing another power generation means such as a piezoelectric element ora thermoelectric conversion element (Peltier element). For example, thepower storage unit 9635 may be charged with a non-contact powertransmission module capable of performing charging by transmitting andreceiving electric power wirelessly (without contact), or any of theother charge means used in combination.

FIG. 24 illustrates other examples of electronic devices. In FIG. 24, adisplay device 8000 is an example of an electronic device including apower storage device 8004 of one embodiment of the present invention.Specifically, the display device 8000 corresponds to a display devicefor TV broadcast reception and includes a housing 8001, a displayportion 8002, speaker portions 8003, and the power storage device 8004.The power storage device 8004 of one embodiment of the present inventionis provided in the housing 8001. The display device 8000 can receiveelectric power from a commercial power supply. Alternatively, thedisplay device 8000 can use electric power stored in the power storagedevice 8004. Thus, the display device 8000 can be operated with the useof the power storage device 8004 of one embodiment of the presentinvention as an uninterruptible power supply even when electric powercannot be supplied from a commercial power supply due to power failureor the like.

A semiconductor display device such as a liquid crystal display device,a light-emitting device in which a light-emitting element such as anorganic EL element is provided in each pixel, an electrophoresis displaydevice, a digital micromirror device (DMD), a plasma display panel(PDP), or a field emission display (FED) can be used for the displayportion 8002.

Note that the display device includes, in its category, all ofinformation display devices for personal computers, advertisementdisplays, and the like besides TV broadcast reception.

In FIG. 24, an installation lighting device 8100 is an example of anelectronic device including a power storage device 8103 of oneembodiment of the present invention. Specifically, the lighting device8100 includes a housing 8101, a light source 8102, and the power storagedevice 8103. Although FIG. 24 illustrates the case where the powerstorage device 8103 is provided in a ceiling 8104 on which the housing8101 and the light source 8102 are installed, the power storage device8103 may be provided in the housing 8101. The lighting device 8100 canreceive electric power from a commercial power supply. Alternatively,the lighting device 8100 can use electric power stored in the powerstorage device 8103. Thus, the lighting device 8100 can be operated withthe use of power storage device 8103 of one embodiment of the presentinvention as an uninterruptible power supply even when electric powercannot be supplied from a commercial power supply due to power failureor the like.

Note that although the installation lighting device 8100 provided in theceiling 8104 is illustrated in FIG. 24 as an example, the power storagedevice of one embodiment of the present invention can be used in aninstallation lighting device provided in, for example, a wall 8105, afloor 8106, a window 8107, or the like other than the ceiling 8104.Alternatively, the power storage device of one embodiment of the presentinvention can be used in a tabletop lighting device or the like.

As the light source 8102, an artificial light source which emits lightartificially by using electric power can be used. Specifically, anincandescent lamp, a discharge lamp such as a fluorescent lamp, andlight-emitting elements such as an LED and an organic EL element aregiven as examples of the artificial light source.

In FIG. 24, an air conditioner including an indoor unit 8200 and anoutdoor unit 8204 is an example of an electronic device including apower storage device 8203 of one embodiment of the present invention.Specifically, the indoor unit 8200 includes a housing 8201, an airoutlet 8202, and the power storage device 8203. Although FIG. 24illustrates the case where the power storage device 8203 is provided inthe indoor unit 8200, the power storage device 8203 may be provided inthe outdoor unit 8204. Alternatively, the power storage devices 8203 maybe provided in both the indoor unit 8200 and the outdoor unit 8204. Theair conditioner can receive electric power from a commercial powersupply. Alternatively, the air conditioner can use electric power storedin the power storage device 8203. Particularly in the case where thepower storage devices 8203 are provided in both the indoor unit 8200 andthe outdoor unit 8204, the air conditioner can be operated with the useof the power storage device 8203 of one embodiment of the presentinvention as an uninterruptible power supply even when electric powercannot be supplied from a commercial power supply due to power failureor the like.

Note that although the split-type air conditioner including the indoorunit and the outdoor unit is illustrated in FIG. 24 as an example, thepower storage device of one embodiment of the present invention can beused in an air conditioner in which the functions of an indoor unit andan outdoor unit are integrated in one housing.

In FIG. 24, an electric refrigerator-freezer 8300 is an example of anelectronic device including a power storage device 8304 of oneembodiment of the present invention. Specifically, the electricrefrigerator-freezer 8300 includes a housing 8301, a door for arefrigerator 8302, a door for a freezer 8303, and the power storagedevice 8304. The power storage device 8304 is provided in the housing8301 in FIG. 24. The electric refrigerator-freezer 8300 can receiveelectric power from a commercial power supply. Alternatively, theelectric refrigerator-freezer 8300 can use electric power stored in thepower storage device 8304. Thus, the electric refrigerator-freezer 8300can be operated with the use of the power storage device 8304 of oneembodiment of the present invention as an uninterruptible power supplyeven when electric power cannot be supplied from a commercial powersupply due to power failure or the like.

Note that among the electronic devices described above, a high-frequencyheating apparatus such as a microwave oven and an electronic device suchas an electric rice cooker require high power in a short time. Thetripping of a breaker of a commercial power supply in use of anelectronic device can be prevented by using the power storage device ofone embodiment of the present invention as an auxiliary power supply forsupplying electric power which cannot be supplied enough by a commercialpower supply.

In addition, in a time period when electronic devices are not used,particularly when the proportion of the amount of electric power whichis actually used to the total amount of electric power which can besupplied from a commercial power supply source (such a proportionreferred to as a usage rate of electric power) is low, electric powercan be stored in the power storage device, whereby the usage rate ofelectric power can be reduced in a time period when the electronicdevices are used. For example, in the case of the electricrefrigerator-freezer 8300, electric power can be stored in the powerstorage device 8304 in night time when the temperature is low and thedoor for a refrigerator 8302 and the door for a freezer 8303 are notoften opened or closed. On the other hand, in daytime when thetemperature is high and the door for a refrigerator 8302 and the doorfor a freezer 8303 are frequently opened and closed, the power storagedevice 8304 is used as an auxiliary power supply; thus, the usage rateof electric power in daytime can be reduced.

This embodiment can be implemented in combination with any of the otherembodiments as appropriate.

Embodiment 6

In this embodiment, examples of vehicles using power storage deviceswill be described.

The use of power storage devices in vehicles enables production ofnext-generation clean energy vehicles such as hybrid electric vehicles(HEVs), electric vehicles (EVs), and plug-in hybrid electric vehicles(PHEVs).

FIGS. 25A and 25B each illustrate an example of a vehicle using oneembodiment of the present invention. An automobile 8400 illustrated inFIG. 25A is an electric vehicle that runs on the power of an electricmotor. Alternatively, the automobile 8400 is a hybrid electric vehiclecapable of driving appropriately using either an electric motor or anengine. One embodiment of the present invention can provide ahigh-mileage vehicle. The automobile 8400 includes the power storagedevice. The power storage device is used not only for driving anelectric motor 8406, but also for supplying electric power to alight-emitting device such as a headlight 8401 or a room light (notillustrated).

The power storage device can also supply electric power to a displaydevice of a speedometer, a tachometer, or the like included in theautomobile 8400. Furthermore, the power storage device can supplyelectric power to a semiconductor device included in the automobile8400, such as a navigation system.

FIG. 25B illustrates an automobile 8500 including the power storagedevice. The automobile 8500 can be charged when the power storage deviceis supplied with electric power through external charging equipment by aplug-in system, a contactless power feeding system, or the like. In FIG.25B, a power storage device 8024 included in the automobile 8500 ischarged with the use of a ground-based charging apparatus 8021 through acable 8022. In charging, a given method such as CHAdeMO (registeredtrademark) or Combined Charging System may be employed as a chargingmethod, the standard of a connector, or the like as appropriate. Theground-based charging apparatus 8021 may be a charging station providedin a commerce facility or a power source in a house. For example, withthe use of a plug-in technique, the power storage device 8024 includedin the automobile 8500 can be charged by being supplied with electricpower from outside. The charging can be performed by converting ACelectric power into DC electric power through a converter such as anAC-DC converter.

Furthermore, although not illustrated, the vehicle may include a powerreceiving device so that it can be charged by being supplied withelectric power from an above-ground power transmitting device in acontactless manner. In the case of the contactless power feeding system,by fitting a power transmitting device in a road or an exterior wall,charging can be performed not only when the electric vehicle is stoppedbut also when driven. In addition, the contactless power feeding systemmay be utilized to perform transmission and reception of electric powerbetween vehicles. Furthermore, a solar cell may be provided in theexterior of the automobile to charge the power storage device when theautomobile stops or moves. To supply electric power in such acontactless manner, an electromagnetic induction method or a magneticresonance method can be used.

According to one embodiment of the present invention, the power storagedevice can have improved cycle performance and reliability. Furthermore,according to one embodiment of the present invention, the power storagedevice itself can be made more compact and lightweight as a result ofimproved characteristics of the power storage device. The compact andlightweight power storage device contributes to a reduction in theweight of a vehicle, and thus increases the mileage. Furthermore, thepower storage device included in the vehicle can be used as a powersource for supplying electric power to products other than the vehicle.In such a case, the use of a commercial power source can be avoided atpeak time of electric power demand.

This embodiment can be implemented in appropriate combination with anyof the other embodiments.

Example 1

In this example, a manufacturing method, analysis results, and the likeof the lithium-containing complex phosphate of one embodiment of thepresent invention will be described.

<Manufacturing Synthetic Material>

The lithium-containing complex phosphate was manufactured on the basisof the flowchart shown in FIG. 2.

As the lithium compound, LiCl was weighed to be 6.359 g in Step S201 a.As the phosphorus compound, H₃PO₄ was weighed to be 3.41 ml in Step S201b. The number of moles of lithium was set to be three times that ofphosphorus. As the solvent, water was weighed to be 50 ml in Step S201d.

Then, LiCl and H₃PO₄ were put into water, so that the mixed solution Awas formed in Step S205. Step S205 was performed in an air atmosphere.Note that while being stirred with a stirring means or the like,materials and the like were put into water during the formation of themixed solution.

Then, as the solution Q, ammonia water with a concentration of 28 wt %was prepared in Step S205 b.

After that, the solution Q was dropped into the mixed solution A and pHmeasurement was performed in Step S207. The solution Q is dropped untilpH becomes a desired one, so that the mixed solution B was formed. Here,several types of mixed solutions B with different pH were prepared. ForpH measurement, a SevenGo Duo pH meter produced by Mettler-ToledoInternational Inc. was used.

Then, as the M(II) compound, FeCl₂.4H₂O was weighed to be 9.941 g inStep S208. The number of moles of iron was equal to that of phosphorus.As the solvent, water was weighed in Step S209 d.

After that, each of the several types of mixed solutions B withdifferent pH was mixed with the mixed solution B, FeCl₂.4H₂O, and water,so that 16 types of solutions in Table 1 were formed as the mixedsolution C in Step S209. Table 1 shows pH of the mixed solution afterStep S207 (mixed solution B), pH after Step S209 (mixed solution C), andpH after Step S211 which will be described later.

TABLE 1 after after after Step S207 Step S209 Step S211 Condition 1 3.992.91 2.42 Condition 2 5.00 3.81 3.48 Condition 3 6.03 4.75 4.00Condition 4 7.01 5.29 4.84 Condition 5 8.09 6.02 5.06 Condition 6 10.009.31 9.40 Condition 7 3.99 2.78 1.81 Condition 8 5.00 3.45 4.24Condition 9 6.02 4.97 4.31 Condition 10 7.94 5.81 5.01 Condition 11 9.017.76 7.84 Condition 12 10.00 9.43 9.09 Condition 13 6.03 3.92 3.39Condition 14 7.07 5.2 3.64 Condition 15 8.16 6.5 6.15 Condition 16 9.999.42 9.34

Then, the mixed solution C was put into an autoclave including an innercylinder made of fluororesin and the mixed solution C was heated at 110°C. for 1 hour as Conditions 1 to 6, at 120° C. for 1 hour as Conditions7 to 12, and at 150° C. for 1 hour as Conditions 13 to 16 in Table 1.During heating, the pressure inside the inner cylinder was approximately0.1 MPa to 0.15 MPa at 110° C. and approximately 0.4 MPa to 0.5 MPa at150° C. After the heat treatment was performed, the heated mixedsolution C was left until the temperature fell and the syntheticmaterial inside the inner cylinder was filtered and the residue waswashed with water. As the autoclave, a mini reaactor MS200-Cmanufactured by OM Lab-Tech Co., Ltd. was used.

Subsequently, the obtained substance was dried in a reduced-pressureatmosphere at 60° C. for two hours, so that a synthetic material A wasobtained.

<XRD Measurement>

The obtained synthetic material A was measured by the XRD θ-2θ method.For the measurement, a D8 ADVANCE manufactured by Bruker AXS was used.

The XRD measurement results of the synthetic materials A obtained underConditions 1, 2, 3, 4, 5, and 6 are shown in FIGS. 26A, 26B, 27A, 27B,28A, and 28B, respectively. Further, FIG. 29A is a partial enlargedgraph of FIG. 27A and FIG. 29B is a partial enlarged graph of FIG. 26B.

Further, the XRD measurement results of the synthetic materials Aobtained under Conditions 7 to 12 are shown in FIG. 30, and the XRDmeasurement results of the synthetic materials A obtained underConditions 13 to 16 are shown in FIG. 31.

In FIG. 29A, six peaks in total having maximum values at 17.1°, 20.7°,25.5°, 29.8°, 32.1°, and 35.6° were observed and the six peakscorrespond to the peaks A to F described in Embodiment 1. It issuggested by these peaks that the synthetic material A obtainedcorresponds to LiFePO₄ of the space group Pnma according to PDF Number01-070-6684 of the International Centre for Diffraction Data (ICDD).Note that PDF Number 01-070-6684 corresponds to Inorganic CrystalStructure Database (ICSD) Code 92198.

Accordingly, lithium iron phosphate having an olivine structure can beformed by controlling pH even at a temperature as low as 110° C. in StepS211.

The degrees of 2θ (A1 to F1) at which the peaks A to F have the maximumvalues were 17.149°, 20.705°, 25.548°, 29.835°, 32.148°, and 35.561° inFIG. 29A. Further, the half widths (A2 to F2) of the peaks were 0.103°,0.063°, 0.087°, 0.227°, 0.144°, and 0.139°. Further, A1 to F1 were17.097°, 20.716°, 25.527°, 29.773°, 32.107°, and 35.530° and A2 to F2were 0.0983°, 0.082°, 0.081°, 0.108°, 0.087°, and 0.095° under Condition9 in FIG. 30. Further, A1 to F1 were 17.210°, 20.767°, 25.610°, 29.876°,32.189°, and 35.602° and A2 to F2 were 0.113°, 0.123°, 0.117°, 0.140°,0.113°, and 0.117° under Condition 10.

In Table 2, W indicates the condition where the most strongly observedpeak of the peaks observed by XRD is any of peaks A to F and X indicatesthe condition where the most strongly observed peak of the peaksobserved by XRD is peaks other than A to F of the peaks observed by XRD.

TABLE 2 Temperture pH after at Step S211 Step S209 W or X Condition 1110° C. 2.91 X Condition 2 3.81 X Condition 3 4.75 W Condition 4 5.29 XCondition 5 6.02 X Condition 6 9.31 X Condition 7 120° C. 2.78 XCondition 8 3.45 X Condition 9 4.97 W Condition 10 5.81 W Condition 117.76 X Condition 12 9.43 X Condition 13 150° C. 3.92 W Condition 14 5.2W Condition 15 6.5 W Condition 16 9.42 X

Here, through detailed analysis of FIG. 29B, slightly weak peaks areobserved, suggesting the correspondence to the peaks B, C, and F. Thus,although the number of by-products is large; however, lithium ironphosphate having an olivine structure that is a target compound is alsoformed under Condition 2, for example.

As shown in Table 2, it is found that a condition in which lithium ironphosphate having an olivine structure can be obtained at any temperaturewhen a pH after Step S209 is less than 5. In other words, the mixedsolution is made acid, so that lithium iron phosphate having an olivinestructure is easily obtained. This is probably because the potential-pHdiagrams of FIG. 6 (Patent Document 1) show that when pH is high and themixed solution is made alkaline, Fe(OH)₂ or the like is generated.Further, it is suggested that when a pH is lower than or equal to 3,lithium iron phosphate having an olivine structure is difficult toobtain in the case where the temperature is low. The lithium ironphosphate dissolves in acid, so that it can be considered that when pHis too low, the lithium iron phosphate is not easily generated.

Further, at 120° C., weak peaks other than those of lithium ironphosphate having an olivine structure were slightly observed in thecondition where a pH was 4.97 in contrast to the condition where a pHwas 5.81. Thus, it can be considered that a higher purity of crystal isobtained under the condition where a pH was 5.81.

In FIG. 28A, peaks were observed at 18.6°, 20.2°, 21.0°, 26.3°, 27.4°,30.4°, and 31.7°. It is suggested that the peaks correspond to the peaksof NH₄FePO₄.H₂O according to the database. Further, in FIG. 28B, peakswere observed at 22.4°, 23.3°, 24.9°, 34.0°, and 36.8°. It is suggestedthat the peaks correspond to the peaks of Li₃PO₄ according to PDF Number00-015-0760. It can be considered that Li₃PO₄ used as the sourcematerial remains. Further, the peak observed at 31.7° may correspond toNH₄FePO₄.H2O according to PDF Number 00-045-0424.

In the case where pH is higher than that in the condition of FIG. 29A,the target synthetic material A is hardly obtained and compounds such asLi₃PO₄ and NH₄FePO₄.H₂O are generated.

Next, the by-product in the case where pH is low is discussed. Peakswere observed at 19.8°, 22.3°, 28.7°, 30.9°, 34.5°, and the like underCondition 8 in FIG. 30 and may correspond to FePO₄.2H₂O of PDF Number00-033-0667, Fe₅P₄O₂₀H₁₀ of PDF Number 00-045-0121, and the like.

<SEM Observation>

Then, SEM observation of the obtained synthetic material A wasperformed. The synthetic material A was obtained as particles. The SEMobservation was performed with S-4800 manufactured by HitachiHigh-Technologies Corporation.

The SEM observation results of the synthetic materials A obtained underConditions 1, 2, 3, 4, 5, and 6 are shown in FIGS. 32A, 32B, 33A, 33B,34A, and 34B, respectively.

The SEM observation results of the synthetic materials A obtained underConditions 7, 8, 9, 10, 11, and 12 are shown in FIGS. 35A, 35B, 36A,36B, 37A, and 37B, respectively.

The SEM observation results of the synthetic materials A obtained underConditions 13, 14, 15, and 16 are shown in FIGS. 38A, 38B, 39A, and 39B,respectively.

As the heating temperature is lower in Step S211, the synthetic materialA that can be obtained is more likely to be a flat-shaped particle. Anexample of the thickness 667 of the synthetic material A and an exampleof the length 666 of the synthetic material A in the case where theheating temperature was 110° C. are shown in FIG. 33A. The thickness 667was approximately 80 nm and the length 666 was approximately 750 nm.Here, the ratio of the thickness 667 to the length 666 is called “aspectratio” in some cases. In the example shown in FIG. 33A, the aspect ratiois low, for example, less than or equal to 0.2. FIG. 36A showsobservation results of the synthetic material A in the case where theheating temperature is 120° C. In FIG. 33A, a flatter (thinner) particlecan be obtained in comparison with FIG. 36A. Further, as in an exampleshown in FIG. 37B in the case where pH is high, it is found that a roundfine particle with a grain size of approximately 100 nm and an aspectratio close to 1 can be obtained. In the case where pH is low, anangular particle can be obtained and the lower the heating temperatureis, the lower the aspect ratio is. Here, the aspect ratio is, forexample, more than or equal to 0.02 and less than or equal to 0.45 ormore than or equal to 0.05 and less than or equal to 0.3.

This application is based on Japanese Patent Application serial no.2016-099458 filed with Japan Patent Office on May 18, 2016, the entirecontents of which are hereby incorporated by reference.

What is claimed is:
 1. A method for manufacturing a positive electrodeactive material comprising lithium, phosphorus, iron, and oxygen,comprising: a first step of forming a first mixed solution by mixing alithium compound, a phosphorus compound, and water; a second step offorming a second mixed solution by adjusting pH by adding a firstaqueous solution to the first mixed solution; a third step of forming athird mixed solution by mixing an iron compound with the second mixedsolution after the second step; and a fourth step of performing heattreatment under a pressure more than or equal to 0.1 MPa and less thanor equal to 2 MPa on the third mixed solution, wherein a pH of the thirdmixed solution is more than or equal to 3.5 and less than or equal to5.0, wherein a highest temperature in the fourth step is more than 100°C. and less than or equal to 119° C., and wherein the positive electrodeactive material belongs to a space group Pnma.
 2. The method formanufacturing a positive electrode active material according to claim 1,wherein the lithium compound is a lithium chloride, wherein the firstaqueous solution is alkaline, and wherein a base included in the firstaqueous solution is ammonia or organic amine.
 3. The method formanufacturing a positive electrode active material according to claim 1,wherein the third step is performed in an air atmosphere.
 4. The methodfor manufacturing a positive electrode active material according toclaim 1, wherein a thickness of a particle of the positive electrodeactive material is more than or equal to 10 nm and less than or equal to200 nm.
 5. A method for manufacturing a positive electrode activematerial comprising lithium, phosphorus, iron, and oxygen, comprisingsteps of: forming a first mixed solution by mixing a lithium compound, aphosphorus compound, and a solvent; forming a second mixed solution byadjusting pH by adding a first aqueous solution to the first mixedsolution; forming a third mixed solution by mixing an iron compound withthe second mixed solution after the step of forming the second mixedsolution; and performing heat treatment under a pressure more than orequal to 0.1 MPa and less than or equal to 2 MPa on the third mixedsolution, wherein a pH of the third mixed solution is more than or equalto 3.5 and less than or equal to 5.0, and wherein a highest temperaturein the heat treatment is more than 100° C. and less than or equal to119° C.
 6. The method for manufacturing a positive electrode activematerial according to claim 5, wherein the solvent comprises water. 7.The method for manufacturing a positive electrode active materialaccording to claim 5, wherein the positive electrode active materialbelongs to a space group Pnma.
 8. The method for manufacturing apositive electrode active material according to claim 5, wherein thelithium compound is a lithium chloride, wherein the first aqueoussolution is alkaline, and wherein a base included in the first aqueoussolution is ammonia or organic amine.
 9. The method for manufacturing apositive electrode active material according to claim 5, wherein thethird mixed solution is formed in an air atmosphere.
 10. The method formanufacturing a positive electrode active material according to claim 5,wherein a thickness of a particle of the positive electrode activematerial is more than or equal to 10 nm and less than or equal to 200nm.